BG64932B1 - Combination of herbicides and safeners - Google Patents

Abstract

Disclosed are herbicidal agents which contain at least one herbicidal active compound of formula and at least one compound used in the protection of cultivated plants. In the formula V stands for optionally substituted rest selected from the group of isoxazole-4-yl, pyrazole-4-yl, cyclohexane-1,3-dione-2-yl and 3-oxopropionitrile-2-yl and R9 stands for nitro, amino, halogen or a radical containing carbon. The group of safeners contains e. g. 2,4-D, cyometrinile, dicamba, dymron, fenclorin, flurazole, fluxofenim, lactidichlorine, MCPA, mecoprop, MG-191, oxabetrinile, methyl- diphenylmethoxyacetate, 1-[4-(N-2-methoxybenzoylsulfamoyl) phenyl]-3-methyl-urea, 1,8-naphthal-acid anhydride, 1-[4-N-2-methoxybenzoylsulfamoyl) phenyl]-3,3-dimethyl-urea, 1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methyl-urea, 1-[4-(N-naphthoylsulfamoyl) phenyl]-3,3-dimethyl-urea, (4-chlorphenoxy) acidic acid, 4-( 2-4-dichlorphenoxy) butyric acid, 4-(4-chlorine-o-tolyloxy) butyric acid, 4-(4-chlorphenoxy) butyric acid, their acids and esters , respectively, N-acylsulfonamide, N-acylsulfamoylbenzoic acid-amides, optionally in form of a salt and optionally substituted1 - phenylpyrazoline-, 1-phenyl pyrazole-, 1-phenyl triazole-, 5-phenylisoxazoline- and 5-phenmylmethylisoxazoline-3-carbonic acid-ester and 2-(8-chinolinyloxy)-acidic-acid- derivatives.

Description

Technical field

The invention relates to the field of plant protection, in particular to combinations of herbicide-antidote (combinations of active substance-safener), which are very suitable for use against competing harmful plants in crops of useful plants.

BACKGROUND OF THE INVENTION

Some novel herbicidally active substances that inhibit p-hydroxyphenylpyruvate dioxygenase (HPPDO) exhibit very good application properties and can be used in very small amounts against a wide variety of grass and broadleaf weeds.

(A)

However, all of these highly active substances are not fully tolerated (ie not sufficiently selective to) by some important crop plants such as maize, rice or cereals, so their use is limited. Therefore, they cannot, or in limited quantities, be used in certain useful crops, so that the desired broad spectrum of herbicidal activity against harmful plants is not achieved. Many of the herbicides mentioned cannot be fully used selectively against pests in maize rice, cereals or other crops.

It is known that a combination of herbicidally active substances with a so-called preservative or antidote is used to overcome these disadvantages. Within the veil (see, for example, R. Prisbylla et al., Brighton Crop Protection Conference - Weeds (193), 731-738).

From US Patents 5,627,131, EP 551650 and EP 298680, known are special mixtures of herbicides and safeners, in particular pre-growth stage safeners.

In addition, it is known from various literature sources that herbicides in the benzoylcyclohexanedione group as inhibitors of p-hydroxyphenylpyruvate dioxygenase have the same mechanism of action as those in the benzoylisoxazole group, compare J. Pesticide Sci. 21, 473-478 (1996), Weed Science 45, 601-609 (1997), Pesticide Science 50, 8384, (1997), and Pesticide Outlook, 29-32, (December 1996). In addition, it is known from Pesticide Science 50, 83-84 (1997) that benzoylisoxazole of formula (A) can, under certain conditions, be rearranged to benzoyl-3-oxopropionitrile (B).

the invention a fuse is a compound or mixture of compounds that remove or diminish the phytotoxic properties of the herbicide relative to beneficial plants without significantly reducing the herbicidal action against harmful plants.

However, finding a fuse for a particular class of herbicide is a difficult task, since the exact mechanisms by which a fuse reduces the harmful effects of herbicides are unknown, the fact that a compound in combination with a particular herbicide does not mean that one compound will also act as a safety net for other classes of herbicides. For example, when using fuses to protect useful plants from herbicidal damage, it has proven that in many cases fuses may show some disadvantages. These include:

- the fuse reduces the action of herbicides against harmful plants,

- the protective properties for beneficial plants are not sufficient in combination with a particular herbicide, the spectrum of beneficial plants using a fuse / herbicide combination is not large enough, 10 one particular fuse cannot be combined with enough a large number of herbicides.

SUMMARY OF THE INVENTION

It is an object of the present invention to find compounds that are suitable in combination with said herbicides to increase the selectivity of these herbicides 20 against important crop plants.

Unexpectedly, a group of compounds was discovered which, together with certain herbicides acting as HPPDO inhibitors, increase the selectivity of these herbicides against important crop plants.

It is therefore an object of the invention to provide a herbicidal agent comprising a mixture of

A. an herbicidal active amount of one or more compounds of formula (I)

where

V means a radical from the group (V1) to (V4),

with symbols and indexes having the following meanings:

R is hydrogen, (C ₁ -C ₄ ) -alkoxycarbonyl, (C ₁ -C ₄ -halogeno-alkoxycarbonyl, (C 1 -C ₄ ) -al- 35 kilsulfonyl, (C ₁ -C ₄ ) -alkylsulfinyl, (C ₁ -C ₄ ) -C 1) alkylthio, COOH, cyano, preferably hydrogen, (C 1 -C ₄ ) -alkoxycarbonyl;

R ¹ is hydrogen, (C 1 -C 4 -alkyl, (C ₂ -C ₄ ) -alkenyl, (C ₂ -C ₄ ) -alkynyl, (C ₃ -C ₈ ) -cycloalkyl, 40 (C ₃ -C) ₈ ) -cycloalkenyl, (C 1 -C ₄ ) alkyl- (C ₃ -C ₈ ) cycloalkyl, (C ₃ -C ₇ ) -halogenocycloalkyl, (C, C ₄ ) -alkylthio- (C ₃ -C ₈ ) - cycloalkyl, (C 1 -C 6 -halogenoalkyl or (C ₂ -C ₈ ) -halogenoalkenyl, preferably (C ₃ -C ₇ ) -cycloalkyl, (C 1 -C 4 -alkyl-N-45 C ₇ ) cycloalkyl;

R ² is hydrogen, (C, -C ₄₎ -alkyl, (Cj-CJ-alkoxy, (C ^ C ^ -haloalkyl, halogen, (C _t -C ₄₎ haloalkoxy, cyano, nitro, preferably hydrogen; 50

R ³ is hydrogen, (C ₁ -C ₄ ) -alkyl, (C ₂ -C ₄ ) -alkenyl, (C ₂ -C ₄ ) -alkynyl, (C 1 -CJ-haloalkyl, (C 1 -C 4 -alkoxy- ^ -C ^ alkyl, (C ^ -CJalkilkarbonil, _{(C] -C4)} -alkyl sulfonyl, (C] _-C4) -halogenoalkilsulfonil with (C] _-C4) -alkyl-substituted or unsubstituted arylsulfonyl, with (C ₁ -C ₄ ) -alkyl substituted or unsubstituted arylcarbonyl- (C ₁ -C ₄ ) -alkyl or with (C 1 -C 4 -alkyl substituted or unsubstituted aryl-C 1 -C 4 -alkyl, preferably hydrogen, (C 1 -C 4) N-alkyl, with (C 1 -C ₄ ) alkyl substituted or unsubstituted arylsulfonyl, (C 1 -C 4 -alkyl-arylcarbonylmethyl, benzyl;

R ⁴ is hydrogen, (C 1 -C ₄ ) -alkyl, (C ₂ -C ₄ ) alkenyl, (C ₂ -C ₄ ) alkynyl, (C 1 -C 4 -halogenoalkyl, phenyl or benzyl, preferably (C ₍ -C ₄ ) -alkyl;

R ⁵ is (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) -alkoxy, (C 1 -C ₄ ) -alkoxy- (C 1 -C ₄ ) -alkyl, (C 1 -C 4 -dialkoxy) (C 1 -C ₄ ) -alkyl, (C ₁ -C ₄ ) -alkylthio, halogen, for local or unsubstituted aryl, tetrahydropyran-4-yl, tetrahydropyran-3-yl, tetrahydrothiopyran-3-yl, 1-methylthio-cyclopropyl, 2-ethylthiopropyl or two radicals R ⁵ together denote (C 2 -C 4) -alkylene, preferably (C 1 -C 6 -alkyl, 5 (C 1 -C 4) -alkoxy, or two R ⁵ denote C 2 -alkenyl;

R ⁶ is hydroxy, (C ₃ -C ₄ ) -alkoxy, (C 1 -C ₈ ) haloalkoxy, formyloxy, (C 1 -C ₄ ) -alkylcarbonyloxy, (C 1 -C ₄ ) -alkylsulfonyloxy, 1 ((C] -C ₄₎ -alkylthio, (C ₁ -C ₄₎ -halogenoalkiltio, arylthio, aryloxy, (C] _-C4) -alkilsufinil or (C _| -C ₄₎ -alkylsulfonyl, preferably hydroxyl, (Cj-C ^ - alkoxy, phenylthio;

R ⁷ is (C 1 -C ₄ ) -alkyl, (C 1 -C 4 -halogenoal-1: kiln, (C ₃ -C ₈ ) -cycloalkyl, (C 1 -C ₄ ) -alkyl (C ₃ -C ₈ ) -cycloalkyl or (C ₃ -C ₈ ) -halo-cycloalkyl, preferably (C ₃ -C ₇ ) -cycloalkyl;

R ⁸ is cyano, (C 1 -C 4 -alkoxycarbonyl, (C ₁ -C ₄ ) -alkylcarbonyl, (C 1 -C 4 -alkylsulfonyl-21 nyl, (C ₁ -C ₄ ) -alkylsulfinyl, (C ₁ -C ₄ ) -alkylthio, (C ₁ -C ₄ ) -alkylaminocarbonyl or (C 1 -CJ-dialkylaminocarbonyl, preferably cyano;

I is an integer from 0 to 6, preferably from 0 to 3, and for 1> 2, the radicals R ⁵ can be 2:

R ⁹ are the same or different and denote nitro, amino, (C 1 -C 4 -alkyl, (C ₂ -C ₄ ) -alkenyl, (C ₂ -C ₄ ) alkynyl, halogen, (C ₁ -C ₄ -haloalkyl, ( C ₂ -C ₄ -halogenoalkenyl, (C ₂ -C ₄ ) haloalkynyl, (C 1 -C ₄ ) -halogenoxy, (C 1 -C ₄ ) haloalkylthio, (C 1 -C ₄ ) -alkoxycarbonyl, (C] - C ₄ ) -alkylsulfonyl, (C ₁ -C ₄ ) -alkylsulfinyl, (C ₁ -C ₄ -alkylthio, arylsulfonyl, arylsulfinyl, arylthio, (C 1 -C ₄ ) -alkoxy, (C 1 -C 4 -alkoxy-CC 4 alkoxy, (C, -C ₄₎ -alkylthio (C] _-C4) -alkoxy, (C] _-C4) -alkylcarbonyl, (Cj-C ^ -alkylaminosulfonyl, (Cj-C ^ -dialkilaminosulfonil, (C ₁ -C ₄₎ alkylcarbamoyl, (C] _-C4) -dialkilkarbamoil, (C] _-C4) -alkyl a _{(C] -C4)} -alkyl, phenoxy, cyano, aryl, alkylamino or dialkylamino, preferably (C] _-C4) -alkyl, halogen, nitro, (C ₁ -C ₄₎ -haloalkyl, (C j- C ₄ ) -halogenoalkoxy, (C ₃ -C ₄ ) -alkylsulfonyl, (C ₁ -C ₄ ) -alkylsulfonyloxy, (C [-C ₄ ) -alkylsulfonylamino, (C 1 -C ₄ ) -alkoxycarbonyl;

q is 0,1,2,3 or 4, preferably 0, 1,2 or 3; and

C. antidote action of one or more fuses in the group:

a) compounds of formulas (II) to (IV) are the same or different, and (R ¹⁷ ) ri

(P)

(Iv) the symbols and indexes have the following meanings:

n 'is an integer from 0 to 5, preferably 0 to 3;

T is a (C 1 or C ₂ ) -alkanediyl chain which is unsubstituted or substituted by one or two (C 1 -C 3 -alkyl radicals or by [(C 1 -C ₃ ) alkoxy] -carbonyl;

W is an unsubstituted or substituted divalent heterocyclic radical of the group of partially unsaturated or aromatic five membered heterocycles with 1 to 3 heteroatoms in the N or O ring, with at least one atom and at most one O atom contained in the ring, preferably a radical of the group (W1) to (W4)

m 'is 0 or 1;

R ¹⁷ , R 7 are the same or different and denote halogen, (C 1 -C 4 -alkyl, (C 1 -C ₄ ) -alkoxy, nitro or (C 1 -C 4 -haloalkyl;

R ¹⁸ , R ²⁰ are the same or different and denote OR ²⁴ , SR ²⁴ or NR ²⁴ R ²⁵ or a saturated or unsaturated 3- to 7-membered heterocycle with at least one N atom and up to 3 heteroatoms, preferably of the O and S group, which is bonded via the N atom to the carbonyl group in (II), resp. (III) and is unsubstituted or substituted by (C 1 -C 4 -alkyl, (C 1 -C 4) -alkoxy radicals or optionally substituted by phenyl, preferably a radical of the formula OR ²⁴ , NHR ²⁵ or N (CH 3 ) ₂ , especially with the formula OR ²⁴ ;

R ²⁴ is hydrogen or unsubstituted or substituted aliphatic hydrocarbon radical, preferably having a total of 1 to 18 C atoms;

R ²⁵ is hydrogen, (C 1 -C ₆ ) -alkyl, (C 1 -C ₆ -alkoxy or substituted or unsubstituted phenyl;

R ²⁶ is hydrogen, (C 1 -C ₈ ) -alkyl, (C ₁ -C ₈ ) -haloalkyl, (C 1 -C 4 -alkoxyC 1 -C 4 -alkyl, (C 1 -C 6 -hydroxyalkyl, (C ₃ -C ₁₂ ) -cycloalkyl or tri- (C ₍ -C ₄ ) -alkyl-silyl;

R ²⁷ , R ²⁸ , R ²⁹ are the same or different and represent hydrogen, (C ₁ -C ₈ ) -alkyl, (C 1 -C ₈ ) -haloalkyl, (C ₃ -C ₁₂ ) -cycloalkyl or substituted or unsubstituted phenyl ;

R ²¹ is (C ₍ -C ₄ ) -alkyl, (C 1 -C 4 -halogenoalkyl, (C ₂ -C ₄ ) -alkenyl, (C ₂ -C ₄ ) -halogenoalkenyl, (C ₃ -C ₇ ) - cycloalkyl, preferably dichloromethyl;

R ²² , R ²³ are the same or different and represent hydrogen, (C ₁ -C ₄ ) -alkyl, (C ₂ -C ₄ ) -alkenyl, (C ₂ -C ₄ ) -alkynyl, (C ₁ -C ₄ ) -Haloalkyl, (C ₂ -C ₄ ) -Haloalkenyl, (C) -C ₄ ) -alkylcarbamoyl (C 1 -C ₄ ) -alkyl, (C ₂ -C ₄ ) -alkenylcarbamoyl- (C _t -C ₄ ) - alkyl, (C ₁ -C ₄ ) -alkoxy- (C ₁ -C ₄ ) -alkyl, dioxolanyl- (C ₁ -C ₄ ) -alkyl, thiazolyl, furyl, furylalkyl, thienyl, piperidyl, substituted or unsubstituted phenyl, or

R ²² and R ²³ together form a substituted or unsubstituted heterocyclic ring, preferably an oxazolidine, thiazolidine, piperidine, morpholine, hexahydropyrimidine or benzoxazine ring;

b) one or more compounds of the group:

1,8-Naphthalic acid anhydride, methyl-diphenylmethoxyacetate, cyanomethoxyimino (phenyl) acetonitrile (Cyometrinil),

1,3-dioxolan-2-ylmethoxyimino (phenyl) acetonitrile (Oxabetrinil),

4'-chloro-2,2,2-trifluoroacetophenoneO-1,3-dioxolan-2-ylmethyloxime (Fluxofenim),

4.6-dichloro-2-phenylpyrimidine (Fenclorim), benzyl-2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate (Flurazole),

2-dichloromethyl-2-methyl-1,3-dioxolane (MG-191),

Ν- (4-ΜβτΗπφβΗΗπ) -Ν '- (1-methyl-1-phenylethyl) urea (Dymron)

- [4- (14-2-methoxybenzoylsulfamoyl) phenyl] -3-methylurea,

1- [4- (b [-2-methoxybenzoylsulfamoyl) phenyl] -3,3-dimethylurea,

1- [4- (N-4,5-dimethylbenzoylsulfamoyl) phenyl] -3-methylurea,

- [4- (N - [naphthoylsulfamoyl) phenyl] -3,3 dimethylurea, (2,4-dichlorophenoxy) acetic acid (2,4-D), (4-chlorophenoxy) acetic acid, (R, S) -2- (4-xnopo-o-TOnHnoKCH) nponHOic acid (Messorgor),

4- (2,4-dichlorophenoxy) butyric acid (2,4-DB), (4-chloro-o-tolyloxy) acetic acid (MCPA),

4- (4-chloro-o-tolyloxy) butyric acid,

4- (4-chlorophenoxy) butyric acid,

3.6-Dichloro-2-methoxybenzoic acid (Dicamba),

- (ethoxycarbonyl) ethyl-3,6-dichloro-2methoxybenzoate (Lactidichlor) as well as their salts, esters, preferably (C 1 -C ₈ );

c) N-acylsulfonamides of formula (V) and their salts,

where

R ³⁰ is hydrogen, a hydrocarbon radical, a hydrocarbon radical, a thiocarbon radical or a heterocyclic radical which is bonded predominantly via a C atom, each of the last 4 radicals mentioned being unsubstituted or substituted by one or more identical or different radicals in the group, halogen, cyano, nitro, amino, hydroxy, carboxy, formyl, carbonamide, sulfonamide and radicals of the formula Z ^a -R ^a , each hydrocarbon hour containing predominantly 1 to 20 C atoms and one C-containing radical R ³⁰ , together with the substituents containing preferably 1 to 30 C atoms;

R ³¹ is hydrogen or (C 1 -C 6 alkyl), preferably hydrogen, or

R3 ° _and R3i h _af e _H o _a group of the formula CO-N- is a radical of a 3- to 8-membered saturated or unsaturated ring;

R ³² is the same or different and stands for halogen, cyano, nitro, amino, hydroxy, carboxy, formyl, CONH ₂ , SO ₂ NH ₂ or a radical of the formula Z ^b -R ^b ;

R ³³ is hydrogen or (C ₁ -C ₄ ) -alkyl, preferably H;

R ³⁴ is the same or different and represents halogen, cyano, nitro, amino, hydroxy, carboxy, CHO, CONH ₂ , SO ₂ NH ₂ or a radical of the formula Z ^c- R ^c ;

R ^a is a hydrocarbon radical or heterocyclic radical, each of the last two mentioned radicals being unsubstituted or substituted by one or more, the same or different radicals in the group halogen, cyano, nitro, amino, hydroxy, mono- and di - [(C , -C ₄ ) -alkyl] -amino, or is an alkyl radical in which several, preferably 2 or 3, non-adjacent CH ₂ groups are respectively replaced by an oxygen atom;

R ^b , R ^c are the same or different and denote a hydrocarbon radical or heterocyclyl, each of the two radicals mentioned above being unsubstituted or substituted by one or more identical or different radicals of the group halogen, cyano, nitro, amino, hydroxy, phosphoryl, halogen - (C ₁ -C ₄ ) -alkoxy, mono-di - [(C 1 -C ₄ ) -alkyl] -amino, or an alkyl radical in which several predominantly 2 or 3, non-adjacent CH ₂ groups are replaced respectively by one oxygen atom;

Z 'is a divalent group of the formula O, S, CO, CS, co-o, co-s, o-co, s-co, so, so ₂ , NR *, CO-NR *, NR * -CO, SO ₂ -NR * or NR * -SO ₂ , as represented on the right by the corresponding divalent group is the bond to R _a , the radicals R * in the last mentioned 5 radicals being independently H, (C 1 -C 4 -alkyl or halo - N - C 1-6 alkyl;

Z ^b , Z ^c are independently a direct bond or a divalent group of the formula O, S, CO, CS, CO-O, CO-S, O-CO, S-CO, SO, SO2, NR *, SO2 -NR *, NR * -SO2, CO-NR * or NR * -CO, where in the case of asymmetric divalent groups the right atom is bonded to the radical R ^b , respectively R ^c and wherein the radicals R * in the last mentioned 5 radicals are independently of one another H, (C1-C4-alkyl or halo-C1-C4) -alkyl;

η is an integer from 0 to 4, preferably 0, 1 or 2, especially 0 or 1, and t is an integer from 0 to 5, preferably 0, 1, 2 or 3, especially 0, 1 or 2;

d) acylsulfamoylbenzoic acid amides of the general formula (VI), optionally in the form of salts

(Vi) where

X ^{3 is} CH or II;

R ³⁵ is hydrogen, heterocyclyl or a hydrocarbon radical, the two last mentioned radicals being optionally substituted by one or more, the same or different radicals of the group halogen, cyano, nitro, amino, hydroxy, carboxy, CHO, CONH ₂ , SO ₂ NH ₂ and Z ^d -R ^d ;

R ³⁶ is hydrogen, hydroxy, (C 1 -C ₆ ) -alkyl, (C ₂ -C ₆ ) -alkenyl, (C ₂ -C ₆ ) -alkynyl, (C 1 -C ₆ ) -alkoxy, (C ₂ -C ₆ -alkenyloxy, the five last mentioned radicals being optionally substituted by one or more, the same or different radicals of the group halogen, hydroxy, (C ₁ -C ₆ alkyl, (C ₁ -C ₄ -alkoxy) and (C ₁ -C ₄ ) -alkylthio, or

R ³⁵ and R ³⁶ together with the nitrogen atom bearing them form a 3- to 8-membered saturated or unsaturated ring;

R ³⁷ is the same or different and represents halogen, cyano, nitro, amino, hydroxy, carboxy, CHO, CONH ₂ , SO ₂ NH ₂ or Z ^is -R ^e ;

R ³⁸ is hydrogen, (C 1 -C ₄ ) -alkyl, (C ₂ -C ₄ ) -alkenyl, (C ₂ -C ₄ ) -alkynyl;

R ³⁹ is the same or different and stands for halogen, cyano, nitro, amino, hydroxy, carboxy, phosphoryl, CHO, CONH ₂ , SO ₂ NH ₂ or Z ^f -R ^f ;

R ^d is a (C ₂ -C ₂₀ ) -alkyl radical whose hydrocarbon chain is interrupted singly or repeatedly by oxygen atoms, heterocyclyl or a hydrocarbon radical, the two last mentioned radicals being optionally substituted by one or more identical or different halogen radicals , cyano, nitro, amino, hydroxy, mono- and di - [(C ₁ -C ₄ ) -alkyl] -amino;

R ^e R ^f are the same or different and denote a (C ₂ -C ₂₀ ) -alkyl radical whose hydrocarbon chain is interrupted singly or repeatedly by oxygen atoms, heterocyclyl or a hydrocarbon radical, the two last mentioned radicals being optionally substituted by one or more the same or different radicals in the group halogen, cyano, nitro, amino, hydroxy, phosphoryl, (C 1 -C ₄ -haloalkoxy, mono- and di - [(C 1 -C ₄ ) -alkyl] -amino;

Z ^d is a divalent radical of the group O, S, CO, CS, C (O) O, C (O) S, SO, SO ₂ , NR *,

C (O) NR * or SO ₂ NR *;

Z ^e , Z ^f are the same or different and denote a direct bond or a divalent radical of the group O, S, CO, CS, C (O) O, C (O) S, SO, S0 ₂ , NR *, SO ₂ NR * or C (O) NR *;

R * is hydrogen, (C 1 -C ₄ ) -alkyl or (C ₁ -C ₄ ) -haloalkyl;

s is an integer from 0 to 4, and o in the case where X is CH means an integer from 0 to 5, and in the case where X is N, denotes an integer from 0 to 4;

including the stereoisomers and the usual agricultural salts, excluding mixtures in which

a) 4- [2-chloro-3- (4,5-dihydroisoxazol3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5 hydroxy-1H-pyrazole and 2,4-D,

4- [2-chloro-3- (4,5-dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy-1H-pyrazole and S-Metolachlor,

4- [2-chloro-3- (4,5-dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy-1H-pyrazole and Dicamba,

4- [2-chloro-3- (4,5-dihydroisoxazol-3 yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy-1H-pyrazole and MCPA,

4- [2-chloro-3- (4,5-dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy-1H-pyrazole and Cloquintocet,

4- [2-chloro-3- (4,5-dihydroisoxazol-3 yl) -4-methylsulfonyl-benzoyl] -1-ethyl-5-hydroxy-1H-pyrazole and Dicamba,

4- [3- (4,5-dihydroisoxazol-3-yl) -2methyl-4-methylsulfonyl-benzoyl] -1-methyl-5 hydroxy-1H-pyrazole and Acetochlor,

4- (3- (4,5-dihydroisoxazol-3-yl) -2methyl-4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy-1H-pyrazole and S-Metolachlor,

4- (3- (4,5-dihydroisoxazol-3-yl) -2methyl-4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy-1H-pyrazole and Dicamba,

(b) in the compound of formula (I) V = VI or V4 and the safener is of formula (IV) or selected from the group of 1,8-naphthalic acid anhydride; methyl-diphenylmethoxy-acetate;

2-dichloromethyl-2-methyl-1,3-dioxolane;

cyanomethoxy-imino (phenyl) -acetonitrile;

1,3-dioxolan-2-ylmethoxyimino- (phenyl) -acetonitrile;

4'-chloro-2,2,2-trifluoroacetophenone-O-

1,3-dioxolan-2-ylmethyloxime;

4,6-dichloro-2-phenylpyrimidine;

benzyl-2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate and

(5-Chloro-8quinolinoxy) acetic acid 1-methyl-hexyl ester;

or

c) in the compound of formula (I) V = V3 with R ⁶ = OH and the safety lock is

- of formula (I) with W = W1, W2, W3 or W4 cm '= I, or

- of formula (III) and T is one (C 1 - or C ₂ -) -alkanediyl chain which is unsubstituted or substituted by one or two (C ₁ -C ₄ ) -alkyl radicals, or

is of formula (IV), or

- compound of the 1,8 naphthalic acid anhydride group, Oxabetrinil, cyanomethoxyimino (phenyl) acetonitrile, Fluxofenim and Flur azole.

In the invention, an herbicidal active amount means an amount of one or more herbicides that may adversely affect plant growth.

In the invention, an antidote active agent is meant an amount of one or more safeners that may at least partially counteract the phytotoxic action of a herbicide or herbicide mixture on a useful plant.

Unless otherwise indicated, the following definitions apply to the radicals in formulas (I) through (VIII) and the following formulas.

The alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio radicals as well as the corresponding unsaturated and / or substituted radicals may be linear or branched in the carbon skeleton. Alkyl radicals, as well as those in complex designations such as alkoxy, haloalkyl, etc., have preferably from 1 to 4 carbon atoms and mean, for example, methyl, ethyl, n- or isopropyl, η-, iso-, tert-or 2-butyl . Alkenyl and alkynyl radicals have the meanings of unsaturated radicals corresponding to the alkyl radicals; alkenyl means for example allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methyl-but-3-en-1-yl and 1-methyl-but-2-en-1-yl. Alkynyl means for example propargyl, but-2in-1-yl, but-3-yn-1-yl, 1-methyl-but-3-yn-1-yl. "(C 1 -C 6 -alkyl" is the short spelling method for alkyl having 1 to 4 C atoms; the same applies to other general definitions of radicals in which the possible number of C atoms is given in parentheses.

Cycloalkyl means preferably one cyclic alkyl radical of 3 to 8, preferably 3 to 7, preferably 3 to 6 C-atoms, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Cycloalkenyl and cycloalkynyl denote the corresponding unsaturated compounds.

Halogen means fluorine, chlorine, bromine or iodine. Haloalkyl, haloalkenyl and haloalkynyl mean substituted by halogen, preferably fluorine, chlorine and / or bromine, especially fluorine or chlorine, partially or fully substituted alkyl, alkenyl or alkynyl, for example CF ₃ , chf ₂ , ch ₂ f, cf ₃ cf ₂ , CH ₂ FCHC1, CC1 ₃ , CHC1 ₂ , CH ₂ CH ₂ C1. Haloalkoxy is, for example, OCF ₃ , ochf ₂ , och ₂ f, cf ₃ cf ₂ o, OCH ₂ CF ₃ and OCH ₂ CH ₂ C1. The same applies to other halogen-substituted radicals.

A hydrocarbon radical may be an aromatic or aliphatic hydrocarbon radical, wherein an aliphatic hydrocarbon radical may be generally linear or branched saturated or unsaturated, hydrocarbon radical, preferably of 1 to 18, especially of 1 to 12 C atoms, for example alkyl, alkenyl or alkynyl.

Preferably an aliphatic hydrocarbon radical means alkyl, alkenyl or alkynyl having up to 12 C atoms; the same applies to an aliphatic hydrocarbon radical in a hydrocarbon oxy radical.

Aryl is generally a mono-di- or polycyclic aromatic system with predominantly 6-20 C atoms, in particular 6-14 C atoms, especially preferably with 6 to 10-C atoms, for example phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentenenyl and fluorenyl, especially preferably phenyl.

Heterocyclic ring, heterocyclic radical and heterocyclyl means a mono-, di or polycyclic ring system which is saturated, unsaturated and / or aromatic and contains one or more, preferably 1 to 4 heteroatoms, preferably of the group N, S and O.

Preferred saturated heterocycles with 3 to 7 ring atoms and one or two heteroatoms in the group О, O and S, wherein the halogens are not adjacent. Particularly preferred are motorcycle rings with 3 to 7 ring atoms and one heteroatom in the group,, O and S, as well as morpholine, dioxolane, piperazine, imidazoline and oxazolidine. The most preferred saturated heterocycles are oxirane, pyrrolidone, morpholine and tetrahydrofuran.

Partially unsaturated heterocycles with 5 to 7 ring atoms and one or two heteroatoms in the Ν, O and S. groups are also preferred. Particularly preferred are unsaturated heterocycles with 5 to 6 ring atoms and one heteroatom of the group N, 0 and S. preferred partially unsaturated heterocycles are pyrazoline, imidazoline and isoxazoline.

Heteroaryl is also preferred, for example mono- or bicyclic aromatic heterocycles with 5 to 6 ring atoms containing one to four heteroatoms in the group О, O, S thereof, the halogens not being adjacent. Particularly preferred are monocyclic aromatic heterocycles with 5 to 6 ring atoms containing one heteroatom of the group О, O and S as well as pyrimidine, pyrazine, pyridazine, oxazole, thiazole, thiadiazole, oxadiazole, pyrazole, triazole and triazole. Pyrazole, thiazole, triazole and furan are most preferred.

Substituted radicals such as substituted hydrocarbons, for example substituted alkyl, alkenyl, alkynyl, aryl such as phenyl and arylalkyl such as benzyl, or substituted heterocyclyl, mean a substituted radical derived from the parent unsubstituted compound, the substituents being preferably one or more, preferably 1, 2 in the case of C1 and F as well as the maximum possible number of substituents of the group halogen, alkoxy, haloalkoxy, alkylthio, hydroxy, amino, nitro, carboxy, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylamino nocarbonyl, substituted amino such as acylamino, mono- and dialkylamino and alkyl sulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, and in the case of cyclic radicals, also alkyl and haloalkostenites; alkynyl, alkenyloxy, alkinyloxy. For radicals with Sutoms, 1 to 4 C atoms, especially 1 or 2 C atoms, are preferred. As a rule, halogen substituents, for example fluorine or chlorine, (C 1 -C ₄ ) -alkyl, preferably methyl or ethyl, (C ₁ -C ₄ ) -haloalkyl, preferably trifluoromethyl, (C 1 -C ₄ ) - alkoxy, preferably methoxy or ethoxy, (C 1 -C ₄ ) -haloalkoxy, nitro and cyano. Methyl, methoxy and chlorine substituents are particularly preferred.

Mono- or disubstituted amino means a chemically stable radical from the group of substituted amino radicals that is N-substituted with, for example, one or two, the same or different radicals from the group alkyl, alkoxy, acyl and aryl; preferably monoalkylamino, dialkylamino, acylamino, arylamino, N-alkyl-N-arylamino, and N-heterocycles. Alkyl radicals having 1 to 4 C atoms are preferred. Aryl is predominantly phenyl. Substituted aryl is preferably substituted phenyl. For acyl, the definition given above is preferably (C ₁ -C ₄ ) -alkanoyl. The same applies to substituted hydroxylamino or hydrazino.

Optionally substituted phenyl means preferably phenyl which is unsubstituted or mono- or polysubstituted, preferably up to three times with halogen such as C1 and F, and also up to five times with the same or different radicals of the halogen group, (C1-CJ-alkyl, ( C 1 -C 4 -alkoxy, (C 1 -C 4 -halogenoalkyl, (C 1 -C ₄ ) -halogenoalkoxy and nitro, for example o, t- and p-tolyl, dimethylphenyl, 2-, 3- and 4-chlorophenyl, 2 , 3- and 4-trifluoro- and trichlorophenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, ο-, m- and p-methoxyphenyl.

An acyl radical means an organic acid radical of up to 6 Satom, for example, a carboxylic acid radical and carboxylic acid derivatives such as thio-carboxylic acids, optionally N-substituted iminocarboxylic acids, or a carbon monoester radical, even carbon monoesters, substituted carbamic acids, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids. Acyl means, for example, formyl, alkylcarbonyl such as (C 1 -C ₄ alkyl) -carbonyl, phenylcarbonyl, the phenyl ring being substituted, for example, as given above for phenyl, or alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl or alkylsulfonyl -alkyl -! - iminoalkyl.

Formulas (I) to (VIII) also cover all stereoisomers having the same topological coupling of atoms and mixtures thereof. Such compounds contain one or more asymmetric C-atoms or double bonds not specifically given in the general formulas.

Possible stereoisomers, defined by their specific spatial form, such as enantiomers, diastereoisomers, Z, - and E-isomers, can be obtained by conventional methods from mixtures of stereoisomers or by stereoselective reactions in combination with stereochemically pure starting materials.

Compounds of general formula (I), which cannot be applied individually or optimally in cereals, rice and / or maize, because they significantly damage crop plants, are suitable as herbicidal active substances according to the invention.

The herbicides of general formula (I) are known, for example, from EP-A 0 137 963, EP-A 0 352 543, EP-A 0 418 175, EP-A 0 496 631 and AU-A 672 058. The compounds of formula (II ) are known, for example, from EP-A 0 333 131 (ZA-1989/01960), EP-A 0 269 806 (US-A-4,891,057), EP-A 0 346 620 (AU-A-1989/034951), EP -A 0 174 562, EP-A 0 346 620, (WO-A-1991/008202), WO-A-1991/007874 or WO-A-1995/007897 (ZA 1994/007120) and references cited therein, and may be prepared by the methods described therein or analogous thereto. The compounds of formula (III) are known from EP-A 0 086 750, EPA 0 94349 (US-A-4,902,340), EP-A 0 191 736 (US-A-4,881,966) and EP-A 0 492 366 and from there cited literature and can be prepared by the methods described or analogous therein.

Some compounds are further described in EP-A-0 582 198. The compounds of formula (IV) are known from numerous patent applications such as US-A-4,021,224 and US-A

4,021,229. The compounds of group (b) are also known from CN-A-1987/010789, EP-A365484, as well as from The Pesticide Manual, The British Crop Protection Council and the Royal Society of Chemistry, 11 ^th edition, Farnham 1997. The compounds of group (c) are described in WOA-1997/045016, those of group (d) are described in German patent application 197 42 951.3, and those of group (e) - in WO-A 1998/013361. The sources cited contain detailed information on methods of preparation and starting materials. These sources are taken into account, they are considered part of this description by citation.

Preference is given to combinations of herbicides, containing fuses of formula (I) and / or (III), where the symbols and indices have the following meanings:

R ²⁴ is hydrogen, (C 1 -C 4 -alkyl, (C ₃ -C ₁₂ ) cycloalkyl, (C ₂ -C ₈ ) -alkenyl and (C ₂ -C ₁₈ ) -alkynyl, the C-containing groups being substituted by one or more, preferably up to three, R ⁵⁰ radicals;

R ⁵⁰ is the same or different and stands for halogen, hydroxy, (C 1 -C 8) -alkoxy, (C 1 -C 8) alkylthio, (C 2 -C 8) -alkenylthio, (C 2 -C 8) -alkynylthio, (C 2 -C 8) -alkenyloxy, (C2-C8) -alkynyloxy, (C3-C7) -cycloalkyl, (C3-C7) -cycloalkoxy, cyano, mono- and di-C 1 -C 6 -alkyl-amino, carboxy, (C 1 -C 8) -alkoxycarbonyl, (C2-C8) -alkenyloxycarbonyl, (C] -C8) -alkylthiocarbonyl, (C2-C8) -alkynyloxycarbonyl, (C1-C4-alkylcarbonyl, (C2-C8) -alkenylcarbonyl, (C2-C8) alkynylcarbonyl, 1- (hydroxyimino) - (C 1 -C 6) -alkyl, 1 - [(C 1 -C 4 -alkylimino] (C 1 -C 4) -alkyl, 1 - [(C 1 -C 4) -alkoxyimino] ( C1-C4-alkyl, (C1-C6-alkylcarbonylamino, (C2-C8) -alkenylcarbonylamino, (C2-C8) -alkynylcarbonylamino, aminocarbonyl, (Cj-C8) alkylaminocarbonyl, di- (C (-C6) -alkyl-aminocarbonyl, (C2-C6) -alkenylaminocarbonyl, (C2-C6) -alkynyl-aminocarbonyl-aminocarbonyl, -Cg) -ankoksikarbonilamino, (C] -C8) -alkilaminokarbonilamino, (C ^ C ^ -alkylcarbonyloxy, which is unsubstituted or is substituted with R ^51, (S2S ₆₎ -alkenilkarboniloksi, (C ₂ -C ₆₎ -alkinilkarboniloksi , (C ₁ -C ₈ ) -alkylsulfonyl, phenyl, phenyl- (C 1 -C ₆ ) -alkoxy, phenyl- (C ₃ -C ₆ ) -alkoxycarbonyl, phenoxy, phenoxy- (C ₁ -C ₆ ) -alkoxy , phenoxy (C ₁ -C ₆₎ -alkoxycarbonyl, phenylcarbonyloxy, phenylcarbonylamino, phenyl (C _[-C6) -alkilka carbonylamino, wherein the last-mentioned 9 radicals are unsubstituted in the phenyl ring or mono- or polysubstituted, preferably up to three times by radicals R ^52; SiR ' ₃ , OsiR' ₃ , R ' ₃ Si- (C ₁ -C _g ) alkoxy, CO-O-NRJ, ON = CR' ₂ , N = CR ' ₂ , 0-NR' ₂ , NR ' ₂ . CH (OR ') ₂ , O- (CH ₂ ) _q -CH (OR') ₂ , CR "'(OR') ₂ , O- (CH ₂ ) _w CR"'(OR") ₂ or c R" OCHR '' CHCOR '- (C ₁ -C ₆ ) -anKOKCH,

R ⁵¹ is the same or different and represents halogen, nitro, (C 1 -C ₄ ) -alkoxy and phenyl, unsubstituted or substituted by one or more, preferably up to three, R ⁵² radicals;

R ⁵² is the same or different and represents halogen, (C 1 -C ₄ ) -alkyl, (C ₁ -C ₄ ) -alkoxy, (C ₁ -C ₄ ) -haloalkyl, (C ₁ -C ₄ ) -haloalkoxy or nitro;

R 'is the same or different and denotes hydrogen, (C 1 -C ₄ ) -alkyl, and phenyl, unsubstituted or substituted by one or more, preferably up to three, radicals R ⁵² , or two radicals R' form together (C ₂ - C ₆ ) -alkanediyl chain;

R 'is the same or different and represents (C 1 -C ₄ ) -alkyl or two radicals

R ' form together a (C ₂ -C ₆ ) -alkanediyl chain;

R '' is hydrogen or (C 1 -C ₄ ) -alkyl;

w is 0, 1, 2, 3, 4, 5 or 6.

Particularly preferred are combinations of herbicide fuse containing fuses of formula (I) and / or (III) where the symbols and indices have the following meanings:

R ²⁴ is hydrogen, (C 1 -C ₈ ) -alkyl, (C ₃ -C ₇ ) cycloalkyl, the foregoing C-containing groups being unsubstituted or substituted once or twice by halogen or once and twice by radicals R ⁵⁰ ,

R ⁵⁰ is the same or different and represents hydroxy, (C 1 -C ₄ ) -alkoxy, carboxy, (C 1 -C ₄ ) alkoxycarbonyl, (C ₂ -C ₆ ) -alkenyloxycarbonyl, (C ₂ -C ₆ ) -alkynyloxycarbonyl , 1- (hydroxyimino) - (C ₁ -C ₄ ) -alkyl, 1 - [(C-C ₄ ) -alkylimino] - (C ₁ -C ₄ ) -alkyl and 1 - [(C [-C ₄ )] -alkoksiimino] (C, -C ₄₎ -alkyl; SiR ' ₃ , ON = CR' ₂ , N = CR ' ₂ , NR' ₂ , ONR ' ₃ , where R' is the same or different and represents hydrogen, (C 1 -C ₄ ) -alkyl or in pairs one (C ₄ -C ₅ ) -alkanediyl chain,

R ²⁷ , R ²⁸ , R ²⁹ are the same or different and represent hydrogen, (C 1 -C ₈ ) -alkyl, (C 1 -C ₆ ) -haloalkyl, (C ₃ -C ₇ ) -cycloalkyl or phenyl, which not substituted or substituted by one or more radicals of the group, halogen, cyano, nitro, amino, mono- and di [(C 1 -C ₄ ) -alkyl] -amino, (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) haloalkyl, (C 1 -C ₄ -alkoxy, (C 1 -C ₄ ) -haloenoxy, (C 1 -C ₄ ) -alkylthio and (C 1 -C ₄ ) -alkylsulfonyl;

R ²⁶ is hydrogen, (C 1 -C ₈ ) -alkyl, (C 1 -C ₈ ) -haloalkyl, (C 1 -C ₄ ) -alkoxy- (C 1 -C ₄ ) -alkyl, (C 1 -C) ₆ ) -hydroxyalkyl, (C ₃ -C ₇ ) -cycloalkyl or tri- (C [-C ₄ ) -alkyl-silyl;

R ¹⁷ , R ¹⁹ are the same or different and denote halogen, methyl, ethyl, methoxy, ethoxy, (C or C ₂ ) -haloalkyl, preferably hydrogen, halogen or (C or C ₂ ) -haloalkyl.

Moreover, fuses are preferred where the symbols and indices in formula (II) have the following meanings:

R ¹⁷ is halogen, nitro or (C 1 -C 6 -halogenalkyl;

n 'is 0, 1, 2 or 3;

R ¹⁸ is a radical of formula OR ²⁴ ,

R ²⁴ is hydrogen, (C 1 -C ₈ ) -alkyl or (C ₃ -C ₇ ) -cycloalkyl, the foregoing C-containing groups being unsubstituted or may be substituted once, repeatedly, preferably up to three times by the same or different halogens groups or up to twice, preferably once with the same or different radicals of the hydroxy, (C 1 -C ₄ ) -alkoxy, (C 1 -C ₄ ) alkoxycarbonyl, (C ₂ -C ₆ ) -alkenyloxycarbonyl group, (C ₂ -C group) ₆ ) -alkynyloxycarbonyl, 1- (hydroxyimino) - (C [-C ₄ ) -alkyl, 1 - [(C [-C ₄ ) -alkylimino] - (C [-C ₄ ) -alkyl, 1 - [(C [-C ₄ ) -alkoxyimino] - (C [-C ₄ ) -alkyl, and radicals of the formula SiR ' ₃ , 0-N = CR' ₂ , N = CR ' ₂ , NR' ₂ and ON-R ' ₂ , wherein the radical R' in the above formulas is the same or different and denotes hydrogen, (C 1 -C ₄ ) -alkyl or in pairs one (C ₄ - or C 1 -C ₆ alkanediyl;

R ²⁷ , R ²⁸ , R ²⁹ are the same or different and represent hydrogen, (C 1 -C ₈ ) -alkyl, (C 1 -C ₆ ) -haloalkyl, (C ₃ -C ₇ ) -cycloalkyl or phenyl which does not is substituted or substituted by one or more radicals, halogen, (C 1 -C ₄ ) alkyl, (C 1 -C ₄ ) -alkoxy, nitro, (C 1 -C ₄ ) -haloalkyl and (C 1 -) C ₄ ) -halogenoalkoxy, and

R ²⁶ is hydrogen, (C 1 -C ₈ ) -alkyl, (C 1 -C ₈ ) -haloalkyl, (C 1 -C ₄ ) -alkoxy- (C 1 -C ₄ ) -alkyl, (C 1 -C) ₆ ) -hydroxyalkyl, (C ₃ -C ₇ ) -cycloalkyl or tri-C 1 -C 4 -alkyl-silyl.

Particularly preferred are fuses of formula (III), where symbols and indices have the following meanings:

R ¹⁹ is halogen or (C ₁ -C ₄ ) -haloalkyl;

n 'is 0, 1, 2 or 3, wherein (R ¹⁹ ) n' is preferably 5-Cl;

R ²⁰ is a radical of the formula OR ²⁴ ;

T is CH ₂ or C 1 -C 10 (C 1 -C 4 -alkyl) and

R ²⁴ is hydrogen, (C ₁ -C ₈ ) -alkyl, (C ₁ -C ₈ ) -haloalkyl or (C ₁ -C ₄ ) -alkoxy- (C ₁ -C ₄ ) -alkyl, preferably (C ₁ - C ₈ ) -alkyl.

Particularly preferred are fuses of formula (II), in which symbols and indices have the following meanings:

W is (W1);

R ¹⁷ is halogen or (C 1 -C 4 -haloalkyl;

n 'is 0, 1,2 or 3, wherein (R ¹⁷⁾ n' is preferably 2,4-C1 _2;

R ¹⁸ is a radical of formula OR ²⁴ ,

R ²⁴ is hydrogen, (C 1 -C ₈ ) -alkyl, (C ₁ -C ₄ -haloenoalkyl, (C ₁ -C ₄ ) -hydroxyalkyl, (C ₃ -C ₇ ) cycloalkyl, (C ₁ -C ₄ -alkoxy- C 1 -C 4 -alkyl or tri- (C ₁ -C ₂ ) -alkylsilyl, preferably (C ₁ -C ₄ ) alkyl;

R ²⁷ is hydrogen, (C 1 -C ₈ ) -alkyl, (C 1 -C 4 -haloalkyl or (C ₃ -C ₇ ) -cycloalkyl preferably hydrogen or (C ₁ -C ₄ ) -alkyl, and

R ²⁶ is hydrogen, (C 1 -C ₈ ) -alkyl, (C ₁ -C ₄ ) -haloalkyl, (C 1 -C ₄ ) -hydroxyalkyl, (C ₃ -C ₇ ) cycloalkyl, (C ₁ -C ₄ ) -alkoxy- (C ₁ -C ₄ ) -alkyl or tri- (C ₁ -C ₂ ) -alkyl-silyl, preferably hydrogen or (C 1 -C 4 -alkyl).

Particularly preferred are herbicidal compositions containing a fuse of formula (II), where symbols and indices have the following meanings:

W is (W 2);

R ¹⁷ is halogen or (C 1 -C ₂ ) -haloalkyl;

n 'is 0, 1, 2 or 3, wherein (R ¹⁷ ) n' is preferably 2,4-Cl ₂ ;

R ¹⁸ is a radical of formula OR ²⁴ ,

R ²⁴ is hydrogen, (C 1 -C 4 alkyl, (C 1 -C ₄ ) -haloalkyl, (C 1 -C ₄ ) -hydroxyalkyl, (C ₃ -C ₇ ) cycloalkyl, (C ₁ -C ₄ ) -alkoxy- (C ₁ -C ₄ ) -alkyl or tri- (C ₁ -C ₂ ) -alkylsilyl, preferably (C ₍ -C ₄ ) alkyl;

R ²⁷ is hydrogen, (C ₍ -C ₈ ) alkyl, (C 1 -C ₄ ) -haloalkyl or (C ₃ -C ₇ ) -cycloalkyl or phenyl, preferably hydrogen or (C ₁ -C ₄ ) -alkyl.

Particularly preferred are fuses of formula (II), where symbols and indices have the following meanings:

W is (W3);

R ¹⁷ is halogen or (C ₁ -C ₂ ) -haloalkyl;

n 'is 0, 1, 2 or 3, wherein (R ^{, 7} ) n' is preferably 2,4-Cl ₂ ;

R ¹⁸ is a radical of formula OR ²⁴ ,

R ²⁴ is hydrogen, (C ^ C ^ -alkyl, (C _t -C ₄₎ -xalogenoalkil, (C ^ C ^ -hydroxyalkyl, (C ₃ -C ₇₎ cycloalkyl, _(Sj-C4) -alkoxy- ( C ₁ -C ₄ ) -alkyl or tri- (C ₁ -C ₂ ) -alkylsilyl, preferably (C 1 -C ₄ ) alkyl, and

R ²⁸ is (C ₁ -C ₈ ) -alkyl or (C 1 -C ₄ ) -haloalkyl, preferably C 1-4 haloalkyl.

Particularly preferred are fuses of formula (II), where symbols and indices have the following meanings:

W is (W4);

R ¹⁷ is halogen, nitro, (C 1 -C 4 -alkyl, (C ₁ -C ₂ ) -haloalkyl, preferably CF ₃ or (C 1 -C ₄ ) -alkoxy;

n 'is 0, 1, 2 or 3;

w 'is 0 or 1;

R ¹⁸ is a radical of formula OR ²⁴ ,

R ²⁴ is hydrogen, (C ₁ -C ₄ ) -alkyl, carboxy (C ₁ -C ₈ ) -alkyl, (C ₁ -C ₄ ) -alkoxycarbonyl (C ₁ -C ₄ -alkyl, preferably (C ₁ -C ₄ ) - alkoxyCO-CH ₂ -, (C ₁ -C ₄ ) -alkoxy-CO-C (CH ₃ ) (H) -, HO-CO-CH ₂ - or HO-CO-C (CH ₃ ) (H) - and

R ²⁹ is hydrogen, (C 1 -C ₆ -alkyl, (C ₁ -C ₄ ) -haloalkyl, (C ₃ -C ₇ ) -cycloalkyl or phenyl which is unsubstituted or substituted by one or more radicals in the group, halogen , (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) -haloalkyl, nitro, cyano and (C 1 -CJ) alkoxy.

The following groups of compounds are particularly suitable as safeners for the herbicidal active substances of formula (I):

a) Compounds of the dichlorophenylpyrazoline-3-carboxylic acid type (i.e., of formula (II), where W = (W 1) and (R ¹⁷ ) _n '= 2,4-Cl ₂ ), preferably compounds such as ethyl ester of 1 (2,4-dichlorophenyl) -5- (ethoxycarbonyl) -5-methyl-2-pyrazoline-3-carboxylic acid (II-1) and related compounds as described in WO13

A 1991/007874;

b) dichlorophenylpyrazolecarboxylic acid derivatives (i.e., of formula (II), where W = (W 2) and (R ¹⁷ ) _n '= 2,4-Cl ₂ ), preferably compounds such as 1- (2, ethyl ester, 4-Dichlorophenyl) -5-methylpyrazole-3-carboxylic acid (II-2), 1- (2,4-dichlorophenyl) -5-isopropylpyrazole-3-carboxylic acid (II-3), ethyl ester of 1 - (2,4-dichlorophenyl) -5- (1,1-dimethylethyl) pyrazole-3-carboxylic acid (II-4), 1 (2,4-dichlorophenyl) -5-phenylpyrazole-3-carboxylic acid ethyl ester (N-5) and related compounds as described in EP-A-0 333 131 and EP-AO 269 806.

c) triazolecarboxylic acid type compounds (i.e., of formula (II), wherein W = (W 3) and (R ¹⁷ ) _n , = 2,4-Cl ₂ ), preferably compounds such as fenchlorazole, i.e. 1- (2,4-Dichlorophenyl) -5-trichloromethyl- (1H) 1,2,4-triazole-3-carboxylic acid ethyl ester (N-6) and related compounds (see EP-A-0 174 562 and EPA-0 346 620);

d) compounds of the type 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid or 5,5-diphenyl-2-isoxazoline-3-carboxylic acid (where W = (W4), preferably compounds such as ethyl ester of 5- (2,4-Dichlorobenzyl) -2-isoxazoline-3-carboxylic acid (II-7) or 5-phenyl-2-isoxazoline-3-carboxylic acid (II-8) ethyl ester and related compounds as described in WO-A 1991/008202, or 5,5-diphenyl-2-isoxazolinecarboxylic acid ethyl ester (II-10) or its n-propyl ester (II-10), or 5- (4-fluorophenyl) -5- phenyl-2-isoxazoline-3-carboxylic acid (II-11) as written in WO-A-1995/007897.

e) 8-quinolinoxyacetic acid type compounds, for example those of formula (III), wherein (R ¹⁹ ) n, = 5-Cl, R ²⁰ = OR ²⁴ and T = CH 2, preferably the compounds

(5-Chloro-8-quinolinoxy) acetic acid (III-1) methyl-hexyl ester,

(5-Chloro-8-quinolinoxy) acetic acid (1H-2), (5-chloro-8-quinolinoxy) acetic acid (3-dimethylbut-1-yl ester),

(5-Chloro-8-quinolinoxy) acetic acid 1-allyloxyprop-2-yl ester, (5-chloro-8-quinolinoxy) acetic acid ethyl ester (III-5), (5- chloro-8-quinolinoxy) acetic acid (III-6), allyl ester of (5-chloro-8-quinolinoxy) acetic acid (III-7),

2- (2-Propylidene-iminoxy) -1-ethyl (5-chloro-8-quinolinoxy) acetic acid (1H-8),

(5-Chloro-8-quinolinoxy) acetic acid (III-9) 2- oxo-prop-1-yl ester and related compounds as described in EP-AO 860 750, EP-A-0 094 349 and EP-A -O 191 736 or EP-A-0 492 366.

f) compounds of the type (5-chloro-8-quinolinoxy) malonic acid, for example those of formula (III), wherein (R ¹⁹ ) _n , = 5-Cl, R ²⁰ = OR ²⁴ and T = -CH (COOO -alkyl), preferably the compounds diethyl ester of (5-chloro-8-quinolinoxy) malonic acid, diallyl ester of (5-chloro-8-quinolinoxy) malonic acid, methyl ethyl ester of (5-chloro-8-quinolinoxy) malonic acid and related compounds as described in EP-A-0 582 198.

g) compounds of the dichloroacetamide type, for example those of formula (IV), preferably:

N, L [-dialyl-2,2-dichloroacetamide (dichlormid from US-A 4,137,070),

4-dichloroacetyl-3,4-dihydro-3-methyl2H-1,4-benzoxazine (benoxacor of EP 0 149 974),

N1, N-diallyl-N-dichloroacetylglycinamide (DKA-24 from HU 2143 821),

4-dichloroacetyl-1-oxa-4-aza-spiro [4,5] decane (AD-67),

2,2-dichloro-L [- (1,3-dioxolan-2-ylmethyl) -N (2-propenyl) acetamide (PPG-1292),

3- dichloroacetyl-2,2,5-trimethyloxazolidine,

3-dichloroacetyl-2,2-dimethyl-5-phenyloxazolidine,

3-dichloroacetyl-2,2-dimethyl-5- (2-thienyl) oxazolidine,

3-dichloroacetyl-5- (2-furanyl) -2,2-dimethyloxazolidine (furilazole, MON 13900),

1-dichloroacetyl-hexahydro-3,3,8-dimethylpyrrolo [1,2-a] pyrimidin-6- (2H) -one (dicyclonon, BAS 145138),

h) compounds of group B (b), preferably 1,8-naphthalic acid anhydride, methyl-diphenylmethoxyacetate, cyanomethoxyimino (phenyl) acetonitrile (cyometrinil),

1,3-dioxolan-2-ylmethoxyimino (phenyl) acetonitrile (oxabetrinil),

4'-chloro-2,2,2-trifluoroacetophenone-O-

1,3-dioxolan-2-ylmethyloxime (fluxofenim),

4.6-dichloro-2-phenylpyrimidine (phenlorim), benzyl-2-chloro-4-trifluoromethyl-1,3 thiazole-5-carboxylate (flurazole),

2-dichloromethyl-2-methyl-1,3-dioxolane (MG-191),

N- (4-methyl phenyl) -N '- (1-methyl-1-phenylethyl) urea (dymron),

1- [4- (L1-2-methoxybenzoylsulfamoyl) phenyl] -3-methylurea,

1- [4- (N-2-methoxybenzoylsulfamoyl) phenyl] -3,3-dimethylurea,

1- [4- (N-4,5-dimethylbenzoylsulfamoyl) phenyl] -3-methylurea,

- [4- (L-naphthoylsulfamoyl) phenyl] -3,3 methyl, (2,4-dichlorophenoxy) acetic acid (2,4-D), (4-chlorophenoxy) acetic acid, (K, 8) -2- (4-chloro-o-tolyloxy) propionic acid (mecoprop),

4- (2,4-dichlorophenoxy) butyric acid (2,4-DB), (4-chloro-o-tolyloxy) acetic acid (MCPA),

4- (4-chloro-o-tolyloxy) butyric acid,

4- (4-chlorophenoxy) butyric acid,

3.6-dichloro-2-methoxybenzoic acid (dicamba),

- (ethoxycarbonyl) ethyl-3,6-dichloro-2-methoxybenzoate (lactidichlor) as well as their salts and esters, preferably (C 1 -C ₈ ).

Compounds of formula (V) and salts thereof are also preferred as safeners

R ³⁰ is hydrogen, (C 1 -C ₆ -alkyl, (C ₃ -C ₆ ) cycloalkyl, furanyl or thienyl, each of the last 4 mentioned radicals being unsubstituted or substituted by one or more radicals in the group, halogen, (C 1-4 -C 1 -alkoxy, halogen-C 1 -C ₄ -alkoxy and (C 1 -C ₄ ) -alkylthio, and in the case of cyclic radicals also with (C ₁ -C ₃ -alkyl and (C ₁ -C ₄ ) - haloalkyl,

R ³¹ is hydrogen,

R ³² is halogen, halogen- (C ₁ -C ₄ ) -alkyl, halogen- (C 1 -C ₄ ) -alkoxy, (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) alkoxy, (C , -C ₄ -alkylsulfonyl, (C [-C ₄ ) -alkoxycarbonyl or (C ₁ -C ₄ ) -alkylcarbonyl, preferably halogen, (C ₁ -C ₄ ) -halogenoalkyl such as trifluoromethyl, (C ₁ -C ₄ ) -alkoxy, halogen-N -C 1 -alkoxy, (C 1 -C 4 -alkoxycarbonyl or (C ₁ -C ₄ ) -alkylsulfonyl,

R ³³ is hydrogen,

R ³⁴ is halogen, (C 1 -C ₄ ) -alkyl, halogen (C ₁ -C ₄ ) -alkyl, halogen- (C ₁ -C ₄ ) -alkoxy, (C ₃ -C ₆ ) -cycloalkyl, phenyl, (C 1 -C ₄ -alkoxy, cyano, (C 1 -C ₄ ) -alkylthio, (C ₍ -C ₄ ) -alkylsulfinyl, (C 1 -C ₄ ) -alkylsulfonyl, (C 1 -C ₄ ) -alkoxycarbonyl or ( C 1 -C ₄ ) -alkylcarbonyl, preferably halogen, (C 1 -C ₄ ) -alkyl, (C ₁ -C ₄ ) -halogenoalkyl such as trifluoromethyl, halogen-N -C 1 -alkoxy, (C 1 -C 4 - alkoxy or (C 1 -C ₄ ) -alkylthio, η is 0, 1 or 2 and tel or 2.

In addition, fuses of formula (VI) are preferred, where

X ³ is CH;

R ³⁵ is hydrogen, (C ₍ -C ₆ ) -alkyl, (C ₃ -C ₆ ) cycloalkyl, (C ₂ -C ₆ ) -alkenyl, (C ₅ -C ₆ ) -cycloalkenyl, phenyl or 3-6 a membered heterocyclyl of up to three heteroatoms from the nitrogen, oxygen and sulfur groups, the last six mentioned radicals being optionally substituted by one or more, the same or different substituents of the halogen, (C 1 -C ₆ ) -alkoxy, (C] - C ₆ -halogaloxy, (C ₁ -C ₂ ) -alkylsulfinyl, (C ₁ -C ₂ ) -alkylsulfonyl, (C ₃ -C ₆ ) -cycloalkyl, (C 1 -C ₄ ) -alkoxycarbonyl, (C ₁ -C ₂ ) alkylcarbonyl and phenyl and in the case of cyclic radicals both with (C 1 -C 4 -alkyl and (C 1 -C ₄ ) -halogenoalkyl;

R ³⁶ is hydrogen, (C 1 -C ₆ ) -alkyl, (C ₂ -C ₆ ) -alkenyl, (C ₂ -C ₆ ) -alkynyl, the three last mentioned radicals being optionally substituted by one or more identical or various radicals from the group halogen, hydroxy, (C 1 -C ₄ alkyl, (C 1 -C ₄ ) -alkoxy and (C 1 -C ₆ -alkylthio);

R ³⁷ is the same or different and stands for halogen, (C ₍ -C ₄ ) -haloalkyl, (C 1 -C ₄ ) -haloalkoxy, nitro, (C ₁ -C ₄ ) -alkyl, (C ₁ -C ₄ -alkoxy) (C ₁ -C ₄₎ -alkylsulfonyl, (C] _-C4) -alkoxycarbonyl or _(C) -C ₄₎ -alkylcarbonyl;

R ³⁸ is hydrogen;

R ³⁹ is the same or different and stands for halogen, nitro (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) -halogen-5-alkyl, (C ₁ -C ₆ -halogenoalkoxy, (C ₃ -C ₆ ) -cycloalkyl , phenyl, (C 1 -C ₄ ) -alkoxy, cyano, (C ₃ C ₄ ) -alkylthio, (C ₁ -C ₄ ) -alkylsulfinyl, (C ₁ -C ₄ -alkylsulfonyl, (C ₁ -C ₄ ) -alkoxycarbonyl or (C 1 -C ₄ ) -alkylcarbonyl; 10 s is 0.1 or 2 and o is 1 or 2.

Of the fuses of formula (VII), the following subgroups are of particular importance:

- compounds wherein R ⁴⁸ and R ⁴⁹ are H, (C 1 -C 4 -alkyl, phenyl, phenyl-N-C 1 -C 6 alkyl, (C 1 -C 4 -alkoxyC 1 -C 4 -alkyl, (C ₃ -C ₆ -alkenyl or (C ₃ -C ₆ ) -alkynyl, the phenyl rings being optionally substituted by F, Cl, Br, NO ₂ , 20 CN, OCH ₃ , (C 1 -C ₄ ) alkyl or CH ₃ -SO ₂ ;

compounds in which R ⁹ is hydrogen;

- compounds in which A is YR ^h ;

- compounds in which E represents oxygen; 25

Table l. (V = Vl):

- compounds in which Q ¹ is CR ₂ ⁴⁷ ;

- compounds in which R ⁴⁷ is hydrogen;

- compounds in which m '= 1 and E represents oxygen or sulfur;

- compounds in which m ”= 0;

- compounds in which R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are hydrogen, E is oxygen, Q ¹ is CR2 ⁴⁷ , A is YR ^h and m ”= 1, especially those in which R ⁴⁷ is H, R ^b is CH 3 and Y is oxygen;

- compounds in which Q ¹ is CR ₂ ⁴⁷ and m 'is 0, especially those in which R ⁴⁴ and R ⁴⁷ are hydrogen and A is YR ^h , with R ^h being predominantly methyl and Y predominantly oxygen.

Preferred groups of herbicides of formula (I) are presented in the following Tables 1 to 4. In them, abbreviations have the following meanings:

c-Pr = cyclopropyl

Et = ethyl

Ph = phenyl

Bz = benzoyl

Methyl

(R ') ₄

Example-Nr. R R ¹ (R ⁹ ) q 1-1 N. c-Rg 2-SO ₂ Me-4-CF ₃ 1-2 N. c-Rg 2-SO ₂ Me-4-CI 1-3 N. c-Rg 2-CI-4-S0 ₂ Me 1-4 N. c-Rg 2-NO ₂ -SO ₂ Me 1-5 N. c-Rg 2,4-Cl ₂ -3-Me 1-6 N. c-Rg 2,4-CI ₂ 1-7 N. c-Rg 2-CI-3-CO ₂ Me-4-SO ₂ Me 1-8 N. c-Rg 2,4-No ₂ 1-9 N. c-Rg 2,4-Br ₂ -3-OCH ₂ SMe 1-10 n c-Rg 2-CP ₃ -4-80gMe 1-11 n c-Rg 2-SO ₂ Me-4-Nr 1-12 n c-Rg 2-CI-3-OEt-4-SO ₂ Et 1-13 n c-Rg 3,4-CI ₂ -SO ₂ Me 1-14 n c-Rg 2-SMe-4-CF ₃ 1-15 n c-Rg 2-SMe-4-Nr

1-16 Η c-Pr 3,4-CI ₂ -2-SMe 1-17 Η c-Pr 4-SF ₅ 1-18 COOEt c-Pr 2-SO ₂ Me-4-CF ₃ 1-19 COOEt c-Pr 2-SO ₂ Me-4-CI 1-20 COOEt c-Pr 2-NO ₂ -4-S0 ₂ Me 1-21 COOEt c-Pr 2,4-CI ₂ -3-Me 1-22 COOEt c-Pr 2,4-No ₂ 1-23 COOEt c-Pr 2,4-Br ₂ -3-OCH ₂ SMe 1-24 COOMe c-Pr 2-SO ₂ Me-4-CF ₃ 1-25 COOMe c-Pr 2-SO ₂ Me-4-CI 1-26 COOMe c-Pr 2-CI-3-CO ₂ Me-4-SO ₂ Me 1-27 H 1-Me-c-Pr 2-SO ₂ Me-4-CF ₃ 1-28 H 1-Me-c-Pr 2-SO ₂ Me-4-CI 1-29 H 1-Me-c-Pr 2-CI-4-S0 ₂ Me 1-30 H 1-Me-c-Pr 2-NO ₂ -4-SO ₂ Me 1-31 H 1-Me-c-Pr 2,4-CI ₂ -3-Me 1-32 H 1-Me-c-Pr 2,4-Clz 1-33 H 1-Me-c-Pr 2-CI-3-CO ₂ Me-4-SO ₂ Me 1-34 COOEt 1-Me-c-Pr 2-CI-3-C0 ₂ Me-4-SO ₂ Me 1-35 COOEt 1-Me-c-Pr 2-SO ₂ Me-4-CF ₃ 1-36 COOEt 1-Me-c-Pr 2-SO ₂ Me-4-CI 1-37 COOEt 1-Me-c-Pr 2-CF4-SO ₂ Me 1-38 COOEt 1-Me-c-Pr 2-NO ₂ -4-SO ₂ Me 1-39 GOD c-Pr 2-SO ₂ Me-4-CF ₃ 1-40 SO ₂ Me c-Pr 2-SO ₂ Me-4-CI 1-41 SOMe c-Pr 2-SO ₂ Me-4-CF ₃ 1-42 SOMe c-Pr 2-SO ₂ Me-4-CI 1-43 SO ₂ Me c-Pr 2-NO ₂ 4-SO ₂ Me 1-44 SOMe c-Pr 2-NO ₂ -4-SO ₂ Me 1-45 SO ₂ Me c-Pr 2-CI-4-SO ₂ Me 1-46 SOMe c-Pr 2-CI-4-SO ₂ Me 1-47 COOMe c-Pr 2-SOMe-4-CF ₃ 1-48 COOEt c-Pr 2-SOMe-4-CF ₃

1-49 Η c-Pr 2-SOMe-4-CF ₃ 1-50 SO ₂ Me 1-Me-c-Pr 2-SO ₂ Me-4-CF ₃ 1-51 SOMe 1-Me-c-Pr 2-SO ₂ Me-4-CF ₃ 1-52 SO ₂ Me 1-Me-c-Pr 2-SO ₂ Me-4-CI 1-53 SOMe 1-Me-c-Pr 2-SO ₂ Me-4-CI

Table 2, (V = V2):

Example-Nr R ² R ³ R4 (R ') q 2-1 H H Et 2-CI-3-OEt-4-S0 ₂ Et 2-2 H H Et 2-SO ₂ Me-4-CF ₃ 2-3 H H Et 2-SO ₂ Me-4-CI 2-4 H H Et 2-SO ₂ Me-4-Nr 2-5 H H Et 2-CF ₃ -4-S0 ₂ Me 2-6 H H Et 2-CI-4-SO ₂ Me 2-7 H H Et 3,4-CI ₂ -2-SO ₂ Me 2-8 H H Et 2-CI-3-COOMe-4-SO ₂ Me 2-9 H H Et 2,4-CI ₂ 2-10 H H Et 2-NO ₂ -4-SO ₂ Me 2-11 H H Et 2,4-Br ₂ -3-OCH ₂ SMe 2-12 H H Et 2,4-No ₂ 2-13 H H Me 2-SO ₂ Me-4-CF ₃ 2-14 H H Me 2-SO ₂ Me-4-CI 2-15 H H Me 2,4-Br ₂ -3-OCH ₂ SMe 2-16 H H Me 2,4-CI ₂ 2-17 H H Me 2-SO ₂ Me-4-CI 2-18 Me CH ₂ -CO- (4-Me- Me 2,4-CI ₂ -CI-3-Me

2-19 Me CH ₂ -CO- (4-Me- Me 2-SO ₂ Me-4-CF ₃ 2-20 Me CH ₂ -CO- (4-Me- Me 2-SO ₂ Me-4-CI 2-21 Me CH ₂ -CO- (4-Me- Me 2,4-Br ₂ -3-OCH ₂ SMe 2-22 Me CH ₂ -CO- (4-Me- Me 2,4-CI ₂ 2-23 Me CH ₂ -CO- (4-Me- Me 2,4-Br ₂ 2-24 Me CH ₂ -CO- (4-Me- Me 2-SO ₂ Me-4-CI 2-25 Me CH ₂ -CO- (4-Me- Me 2-CI-3-COOMe-4-SO ₂ Me 2-26 Me CH ₂ -CO- (4-Me- Me 2-NO ₂ -4-SO ₂ Me 2-27 Me SO ₂ - (4-Me-Ph) Me 2,4-CI ₂ 2-28 Me SO ₂ - (4-Me-Ph) Me 2,4-Br ₂ 2-29 Me SO ₂ - (4-Me-Ph) Me 2,4-CI ₂ -3-Me 2-30 Me SO ₂ - (4-Me-Ph) Me 2-SO ₂ Me-4-CF ₃ 2-31 Me SO ₂ - (4-Me-Ph) Me 2-SO ₂ Me-4-CI 2-32 Me SO ₂ - (4-Me-Ph) Me 2,4-Br ₂ -3-OCH ₂ SMe 2-33 Me SO ₂ - (4-Me-Ph) Me 2-NO ₂ -4-SO ₂ Me 2-34 Me CH ₂ -CO-Ph Me 2,4-CI ₂ 2-35 Me CH ₂ -CO-Ph Me 2,4-CI ₂ -3-Me 2-36 Me CH ₂ -CO-Ph Me 2-SO ₂ Me-4-CF ₃ 2-37 Me CH ₂ -CO-Ph Me 2-SO ₂ Me-4-CI 2-38 Me CH ₂ -CO-Ph Me 2,4-Br ₂ -3-OCH ₂ SMe 2-39 Me CH ₂ -CO-Ph Me 2-CI-3-COOMe-4-SO ₂ Me 2-40 Me CH ₂ -CO-Ph Me 2,4-No ₂ 2-41 Me CH ₂ -CO-Ph Me 2-NO ₂ -4-SO ₂ Me 2-42 H Bz Me 2,4-CI ₂ 2-43 H Bz Me 2,4-CI ₂ -3-Me 2-44 H Bz Me 2-SO ₂ Me-4-CF ₃ 2-45 H Bz Me 2-SO ₂ Me-4-CI 2-46 H Bz Me 2,4-No ₂ 2-47 H Bz Me 2-NO ₂ -4-SO ₂ Me 2-48 H Bz Me 2-CI-3-COOMe-4-SO ₂ Me 2-49 H Bz Me 2,4-Br ₂ -3-OCH ₂ SMe

Table 3 _r (V = V3):

Ο

Example-Nr. (R ^s ) i R ⁶ (R ') q 3-1 HE 2-CI-4-SO ₂ Me 3-2 HE 2-NO ₂ -4-SO ₂ Me 3-3 HE 2,4-CI ₂ 3-4 HE 2,4-No ₂ 3-5 HE 2,4-CI ₂ -3-Me 3-6 HE 2,4-Br ₂ -3-OCH ₂ SMe 3-7 HE 2-SO ₂ Me-4-C! 3-8 HE 2-SO ₂ Me-4-CF ₃ 3-9 HE 2-SO ₂ Me-4-Nr 3-10 HE 2-C! -3-COOMe-4-SO ₂ Me 3-11 he 2-NO ₂ -4-OCF ₂ H 3-12 4,4- (Me) ₂ he 2-NO ₂ -4-OCF ₂ H 3-13 4,4- (Me) ₂ he 2-CI-4-SO ₂ Me 3-14 4.4- (Me) ₂ he 2-NO ₂ -4-SO ₂ Me 3-15 4.4- (Me) ₂ he 2,4-CI ₂ 3-16 4.4- (Me) ₂ he 2-C! -3-COOMe-4-SO ₂ Me 3-17 4.4- (Me) ₂ he 2,4-Br ₂ -3-OCH ₂ SMe 3-18 4.4- (Me) ₂ he 2-SO ₂ Me-4-CI 3-19 4.4- (Me) ₂ he 2-SO ₂ Me-4-CF ₃ 3-20 4.4- (Me) ₂ he 2,4-CI ₂ -3-Me 3-21 4.4- (Me) ₂ he 2,4-No ₂ 3-22 4-CH ₂ -CH ₂ -6 SPh 2-CI-4-SO ₂ Me 3-23 4-CH ₂ -CH ₂ -6 SPh 2,4-Cl ₂ -3-Me 3-24 4-CH ₂ -CH ₂ -6 SPh 2,4-Br ₂ -3-OCH ₂ SMe 3-25 4-CH ₂ -CH ₂ -6 SPh 2-NO ₂ -4-SO ₂ Me

3-26 4-CH ₂ -CH ₂ -6 SPh 2,4-CI ₂ 3-27 4-CH ₂ -CH ₂ -6 SPh 2-SO ₂ Me-4-CI 3-28 4-CH ₂ -CH ₂ -6 SPh 2,4-No ₂ 3-29 4-CH ₂ -CH ₂ -6 SPh 2-CI-3-COOMe-4-SO ₂ Me 3-30 4-CH ₂ -CH ₂ -6 SPh 2-SO ₂ Me-4-CF ₃ 3-31 5.5- (Me) ₂ OH 2-NO ₂ -4-OCF ₂ H 3-32 5.5- (Me) ₂ OH 2-CI-4-SO ₂ Me 3-33 5.5- (Me) ₂ OH 2-NO ₂ -4-SO ₂ Me 3-34 5.5- (Me) ₂ OH 2-CI-3-COOMe-4-SO ₂ Me 3-35 5.5- (Me) ₂ OH 2,4-CI ₂ -3-Me 3-36 5.5- (Me) ₂ OH 2,4-CI ₂ 3-37 5.5- (Me) ₂ OH 2,4-No ₂ 3-38 5.5- (Me) ₂ OH 2,4-Br ₂ -3-OCH ₂ SMe 3-39 5.5- (Me) ₂ OH 2-S0 ₂ Me-4-CI 3-40 5.5- (Me) ₂ OH 2-SO ₂ Me-4-CF ₃

Table 4: (V = V4):

ο

Example-Nr. R ⁷ R ⁸ (R ') q 4-1 c-Pr CN 2-C! -3-OEt-4-SO ₂ Et 4-2 c-Pr CN 2-SO ₂ Me-4-CF ₃ 4-3 c-Pr CN 2-SO ₂ Me-4-CI 4-4 c-Pr CN 2-SO ₂ Me-4-Nr 4-5 c-Pr CN 2-CF ₃ -4-S0 ₂ Me 4-6 c-Pr CN 2-Cl-4-SO ₂ Me 4-7 c-Pr CN 3,4-CI ₂ -2-SO ₂ Me 4-8 c-Pr CN 2,4-Cl _z 4-9 c-Pr CN 2,4-No ₂

4-10 c-Rg CN 2-CI-3-COOMe-4-SO ₂ Me 4-11 c-Rg CN 2,4-C1 ₂ -3-Me 4-12 c-Rg CN 2,4-Br ₂ -3-OCH ₂ SMe 4-13 c-Rg CN 2-NO ₂ -4-SO ₂ Me

Antidotes of formulas (II) to (VII), as well as compounds of group j (b), exemplary safeners of the above groups a) to b), reduce or prevent the phytotoxic effects that may occur with the use of herbicides active substances of formula (I) in cultivated plants without significantly affecting the activity of these active substances against harmful plants. Thus, the scope of conventional plant protection products can be significantly expanded to include crops such as wheat, barley, maize, rice and other crops where the use of herbicides has not been possible or possible on a limited scale so far. that is, in small doses there is a small spectrum of action.

The herbicidal mixtures according to the invention and the aforementioned safeners can be applied together (as a ready-made preparation or by the tank-mixing method) or one after the other in any order. The weight ratio of fuse: herbicide may vary widely, and is preferably in the range 1: 100 to 100: 1, especially from 1:10 to 10: 1. The optimal amounts of herbicide and fuse depend on the type of herbicide used or the fuse used, as well as on the plants being treated, and can be determined on a case-by-case basis by appropriate preliminary experiments.

The main areas of application of the combinations according to the invention are first of all corn and cereals (eg wheat, rye, barley, oats), rice, sorghum or cotton and soybeans, mainly cereals, rice and corn.

The fuses of the invention can be used according to their properties for the pre-treatment of the seed of the crop (seed decontamination) or placed in the seed crop before sowing, or together the herbicide is applied before or after the emergence of the plants. Pre-emergence treatment includes both cultivation of arable land before sowing and cultivation of cultivated arable land. Co-administration with herbicide is preferred. Tank mixes or formulations may be used.

The required consumption rates for fuses may vary depending on the indication and the herbicide used over a wide range and are generally in the range of 0.001 to 5 kg, preferably 0.005 to 0.5 kg of active substance per hectare.

It is also an object of the invention to protect crop plants from the phytotoxic side effect of the herbicides of formula (I), which consists in the fact that an antidote action of a compound of formula (II) is applied to the plants, seeds or cultivated area , (III), (IV), (V), (VI), (VII) and / or (of group b)), before, after or together with the herbicidally active substance A of formula (I).

The herbicide-fuse combinations according to the invention can be used to control harmful plants in crops of plants known or already developed by the genetic engineering. Transgenic plants have particularly favorable properties, such as resistance to certain plant protection products, resistance to plant diseases or pathogens such as certain insects or certain microorganisms such as fungi, bacteria and viruses. Other characteristic properties include e.g. to harvest is the quantity, quality, storage capacity, composition and special ingredients. Thus, transgenic plants are known to have increased starch content or altered starch quality, or a different fatty acid composition in the crop.

The use of the combinations according to the invention in transgenic crops of economic importance - useful plants and ornamental plants, such as cereals such as wheat, barley, rye, oats, millet, rice, cassava and maize or sugar beet, cotton, soybean, rape , potatoes, tomatoes, peas and more. varieties of vegetables.

In the application of the combinations of the invention to transgenic crops, in addition to the observed effects on harmful plants in other crops, actions that are specific to the application in the respective transgenic culture, for example a modified or specifically expanded spectrum of harmful crops that can occur, often occur destroy, altered application rates, such as good ability to combine with herbicides to which transgenic crops are resistant, as well as impact on growth and yield of the transgenic crop plants.

It is therefore an object of the invention to use the combinations according to the invention to control harmful plants in transgenic crops.

The safeners of formulas (III) - (VII) and of group (b) and their combination with one or more of the said herbicides of formula (II) may be formulated differently depending on the biological and / or physicochemical parameters specified. . Possible formulations are, for example: spray powders (WP), emulsifiable concentrates (EU), water-soluble powders (SP), water-soluble concentrates (SL), concentrated emulsions (BW) such as oil-in-water and water-in-oil emulsions, solutions or spray emulsions, capsule suspensions (CS), oil or water-based dispersions (SC), suspoemulsions, suspension concentrates, dusting agents (DP), oil-soluble solutions (OL), disinfectants, granules (GR) in the form of microgranules, spray granules, cover granules and adsorption granules, granules for soil application or for broadcasting, water-soluble granules (SG), water dispersible granules (WG), ULVformulirovki, microcapsules and waxes.

These individual formulations are generally known and are described, for example, in: Winnacker-Koechler, Chemische Technologie Band 7, C. Hauser Verlag Muenchen, 4th Aufl., 1986; Wade van Valkenburg, “Pesticide Formulations” by Marcel Dekker Ν. Y., 1973; K. Martens, “Spray Drynd Handbook”, 3rd ^ed . 1979, G. Goodwin Ltd. London.

Necessary formulation aids such as aggregates, surfactants, solvents and other additives are also known and are described, for example, in: Watkins Handbook of Insecticide Dust Diluents and Carriers, 2 nd Ed., Darland Books, Caldwell NJ; H. v. Olphen, “Introduction to Clay Colloid Chemistry,” 2 nd Ed., J. Wiley & Sons, Ν. Y .; N. Marsden “Solvents Guide, 2 ^nd Ed., Interscience, Ν. Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual," MC Publ. Corp., Ridgewood NJ; Sisley and Wood, “Encyclopedia of Surface Active Agents,” Chem. Publ. Co. Inc., Ν. Y. 1964; Schoenfeld, “Grenzflaechenaktive Aethylenoxidaddukte”, Wiss. Verlagsgesell., Stuttgart 1976; WinnackerKuechler “Chemische Technologie”, Band 7, C. Hauser Verlag Muenchen, 4th Aufl. 1986.

Based on these formulations, combinations with other plant protection agents, such as insecticides, acaricides, herbicides, fungicides, as well as with crop protection agents, fertilizers and / or growth regulators, for example in the form of a ready-made formulation or as a tank mixture, may be obtained .

Spray powders are preparations that are dispersed uniformly in water which, together with the active substance, in addition to the diluent and inert material, also contain ionic and / or non-ionic (cross-linking, dispersing) surfactants, for example polyoxyethylated alkylphenols, polyoxystyrenes , fatty alcohol polyglycolsulfates, alkanesulfonates, alkylbenzosulfonates, sodium ligninsulfonate, sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, sodium dibutyl naphthalenesulfonate or sodium ole lmetiltaurinat. For the preparation of dusting powders, the herbicidal active substances are mixed, for example, in conventional apparatus such as quenching mills, blower mills and air-jet mills.

Emulsifiable concentrates are prepared, for example, by dissolving the active substance in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene, or also high boiling hydrocarbons such as aromas, saturated or unsaturated aliphatic or alicyclics, or mixtures of organic solvents with several solvents of ionic and / or non-ionic type (emulsifiers). as emulsifiers may be used, for example: calcium (C ₆ -C ₁₈ -alkyl aryl sulfonates such as Ca-dodecylbenzenesulfonate or non-ionic emulsifiers such as fatty acid polyglycolesters, (C ₂ -C ₁₈ ) alkylarylpolyglycolide, polyglycolyzol fat products, and ethylene oxide, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters or polyoxyethylene sorbitan or other polyoxyethylene sorbitan fatty acid esters.

Dusting agents are obtained by grinding the active substance with finely dispersed solids, for example talc, natural clays such as kaolin, bentonite and pyrophyllite or diatomite.

The suspension concentrates may be water or oil based. They can be obtained, for example, by wet milling in commercially available pearl mills and optionally by the addition of surfactants, such as those mentioned in other formulations.

Emulsions, e.g. of oil-in-water (EW) can be obtained, for example, by stirring, colloidal mills and / or static mixing using water-soluble organic solvents and optionally surfactants, such as those mentioned in other formulations.

The granules are obtained either by spraying the active substance on a granular inert material with adsorption capacity or by applying the concentrate of the active substance by adhesive substances, for example polyvinyl alcohol, sodium polyacrylate or also mineral oils on the surface of carriers such as sand, kaolinite or surface of granules. inert material. Suitable active substances may also be granulated in the usual manner to obtain the granules from the fertilizer method - optionally in admixture with fertilizers. Water-dispersible granules are prepared by conventional methods such as spray drying, fluidized bed granulation, disk granulator, mixing with high-speed mixers and extrusion without solid inert material. For the preparation of the disk granulator granule in the fluidized bed by extrusion and dispersion, see, for example, “Spray-Drying Handbook” 3rd ed. 1979, Goodwon Ltd., London; JE Browning, “Agglomeration'Chemical and Engineering” 1967, Seiten 147 ff; Perry's Chemical Engineer's Handbook 5 ^th Ed., McGraw-Hill, Ν. Y. 1973, S. 8-57.

For further details on the formulation of plant protection products, see, for example, G. S. Klingmann, "Weed Control as a Science," John Wiley and Sons, Inc., New York, 1961, pp. 81-96, and J. D. Freyer, S.A. Evans: Weed Control Handbook, 5 ^th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101103.

Agrochemicals generally contain 0.1 to 99% by weight, especially 0.1 to 95% by weight of active substances of formula (II) - (VII) and / or (b) or the active herbicide / antadot mixture (I) and (II) - ( VII) and / or (b) and 1 to 9.9% by weight, especially 5 to 99.8% by weight of solids or liquid excipients and 0 to 25% by weight, especially 0.1 to 25% of surfactants.

In spraying powders, the concentration of active substances is from 10 to 90% by weight, and the remainder up to 100% consists of the formulation component which is customary. For emulsifiable concentrates, the concentration of the active substance may be from 1 to 80 wt. %. The powdered formulations contain 1 to 20% by weight of active substances, the spray solutions contain from 0.2 to 20% by weight of active substances. In the case of the granules as dispersible, the granules of the active substance depend in part on whether the active substance is liquid or solid. Generally, the content of the active substance of the water-dispersible granules is between 10 and 90% by weight.

In addition, said active ingredient formulations contain, as appropriate, the customary conventional adhesives, wetting agents, dispersants, emulsifiers, penetrators, preservatives, antifreeze agents and solvents, fillers, colorants and carriers, dehumidifiers, evaporation and pH inhibitors, regulators.

For example, known active substances, such as those described in, for example, Weed Research 26, 441-445 (1986) or The Pesticide Manual, 10 ^th edition, The may be used as combination partners for the mixtures according to the invention. British Crop Protection Counssil, 1994 and in the literature cited therein. As known from the literature, herbicides that can be combined with the mixtures of the invention may mention, for example, the following active substances (note: the compounds are mentioned either by their "trivial names" according to the International Standards Organization (ISO) or by chemical names, possibly together with the usual code number):

acetochlor; acifluorfen; aclonifen; AKH 7088, i.e. [[[1- [5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrophenyl] -2-methoxyethylidene] -amino] oxy] acetic acid and its methyl ester; alachlor; aloxidime; ametrine; amidosulfuron; amitrol; AMS, i.e. ammonium sulfate; anilofos; assulam; atracin; azafenidine (DPX-R6447), azimsulfuron (DPXA8947); aziprotrin; barban; BAS 516H, i.e. 5fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; benazoline; benfluralin; benfuresate; bensulfuron-methyl; benzulide; bentazone; benzofluorine; benzoylprop-ethyl; benzthiazuron; bialaphos; bifenox; bispyribac sodium (KIH-2023), bromacil; bromobutide; bromophenoxime; bromoxynil; bromuron; buminafos; busoxinone, butachlor; butamifos; butenechlor; butidazole; butralin; butroxidime (ICI-0500), butylate; kaffenstrol (CH-900); carbetamide; cafentrazone; CDAA, i.e. 2-chloro-H, L1-di-2-propenylacetamide; CDEC, i.e. diethyldithiocarbamic acid 2-chloroallyl ester; chlomethoxyfen; chloramben; chlorosulam-methyl (XDE565); chlorazifop-butyl, chlorobromuron; chlorine buffered; chlorofenac; chlorofluorecol-methyl; chloridazone; chlorimuron ethyl; chlornitrofen; chlorotholuron; chloroxuron; chlorpropham; chlorosulfuron; chlorthal-dimethyl; chlorthiamide; cinidon-ethyl; cinmethylin; cinosulfuron; cletodim; clodinafop and its ester derivatives (eg clodinafop-propargyl); clomazone; clomeprop; cloproxidime; clopyralide; cumyluron (JC 940); cyanazine; cycloate; cyclosulfamuron (AC 014); cycloxydim; cycluron; cyhalophop and its ester derivatives (eg DEH-112 butyl ester); cyperquat; cyprazine; cyprazole; 2,4-DB; dalapone; desmedifam; desmethrin, dialate; dicamba; dichlobenyl; dichloroprop; diclofop and its esters such as diclofop-methyl; diclosulam (XDE564), diethyl; diphenoxuron; difenzoquat; diflufenican; diflufenzopyr sodium (SAN835H), dimefuron; dimethachlor; dimethamethrin; dimethenamide (SAN-582H); dimethazone, 5- (4,6-dimethylpyrimidin-2-ylcarbamoylsulfamoyl) -1- (2-pyridyl) pyrazole methyl ester-

4- carboxylic acid (NC-330); triaziflam (IDH-1105), clomazone; dimethipine; dimetrazulfuron, dinspramine; dinoseb; dinoterb; diphenamide; dipropetrin; diquat; dithiopyr; diuron; DNOC; eglinazine-ethyl; EL 177, ie

5- cyano-1- (1,1-dimethylethyl) -N-methyl-1H-pyrazole-4-carboxamide; endotal; epoprodan (MK-243), EPTC; esprocarb; ethfluralin; ethamethsulfuron-methyl; ethidimuron; ethiozine; ethofumesate; F5231, i.e. 14- [2-chloro-4-fluoro-5- [4- (3-fluoropropyl) -4,5-dihydro-5-oxo-1H-tetrazol-1-yl] -phenyl] ethanesulfonamide; ethoxyphene and its esters (eg ethyl ester, HN-252); ethoxysulfuron (from EP 342569) ethobenzanide (HW 52); 3- (4-ethoxy-6-ethyl 1,3,5-triazin-2-yl) -1- (2,3-dihydro-1,1-dioxo-2-methylbenzo [b] thiophene-7-sulfonyl) - urea (EP-A 079 683); 3- (4-ethyl-6-methoxy-1,3,5triazin-2-yl) -1- (2,3-dihydro-1,1-dixo-2-methylbenzo [b] thiophene-7-sulfonyl) urea (EP-A 079 683); fenoprop; phenoxane; phenoxaprop and phenoxaprop-P as well as its esters, e.g. phenoxaprop-β-ethyl and phenoxaprop-ethyl; phenoxidime; fenuron; flamprop-methyl; flasasulfuron; flufonacet (VAU-ROE-5043), fluazifop and fluazifop-P, florasulam (DE-570) and its esters, e.g. fluazifop-butyl and fluazifop-P-butyl; fluchloraline; flumetsulam;

flumeturon; flumiclorac and its esters (e.g., pentyl ester, S-23031); flumioxazine (S-482); flumipropine; flupoxam (KNW739); fluorodifene; fluoroglycophene-ethyl; flupropacil (UBIC-4243); flupyrsulfuromethyl sodium (DPX-KE459), fluridone; fluorochloridone; fluroxypyr; flurtamone; flutiacet-methyl (KS-9201), fomezaphene; fosamine; furiloxifene; glufosinate; glyphosate; halozafen; halosulfuron; and esters thereof (e.g., methyl ester, NC-319); haloxyfop and its esters; haloxyfop-P (= Khaloxyfop) and its esters; hexazinone; imazamethabenz-methyl; imazamox (AC-292263), imazapyr; imazachine and salts such as ammonium salt; imazetamethapyr; imazethapyr; imazosulfuron; iodosulfuron (methyl-4-iodo-2- [3- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) ureidosulfonyl] -benzoate, sodium salt, WO 1992/013845); zoxinyl; isocarbamide; isopropalin; isoproturon; isouron; isoxaben; isoxapyrifop; carbutylate; lactophen; lenacil; linuron; MPA; HRW; mecoprop; mefenacet; mefluidide; metamitron; metazachlor, metabenzthiazuron; metam; metazole; methoxyphenone; methyldimron; metabenzuron; methyl-2- [3- (4,6-dimethoxypyrimidin-2yl) ureidosulfonyl] -4-methanesulfonamido-methylbenzoate (W01995 / 010507); metobenzuron; methobromuron; metolachlor; 5-metolachlor, metosulam (XRD 511); methoxuron; metribuzin; metsulfuron-methyl; MH; molinate; monalide; monocarbamide dihydrogen sulfate; monolinuuron; monuron;

MT 128, i.e. 6-chloro-N- (3-chloro-2-phenyl) -5-methyl-N-phenyl-3-pyridazinamine; MT 5950, i.e. N- [3-chloro-4- (1-methylethyl) -phenyl] -2-methylpentanamide; N, N-dimethyl-2- [3 (4,6-dimethoxypyrimidin-2-yl) ureidosulfonyl] -4-formylamino-benzamide (WO 1995/001344); naproanilide; napropamide; napaltam; NC 310, i.e. 4- (2,4-dichlorobenzoyl) -1-methyl5-benzyloxypyrazole; neuron; nicosulfuron; nipiraclofen; nitralin; nitrofen; nitrofluorfen; norflurazone; orbencarb; rhizalin; oxadiargyl (RP-020630); oxadiazone; oxacyclomephone (ΜΥ-100), oxyfluorfen; oxasulfuron (CGA-277476), paraquat; pebulate; pendimethalin; pentoxazone (KRP-314), perfluidone; phenisofam; fenmedifam; picloram; piperaphos; pyributicarb; pyrifenop-butyl; pretachlor; primisulfuron-methyl; procyazine; prodiamine; profluralin; proglinazine-ethyl; prometone; promethrin; propachlor; propanyl; propachisafop and its esters; propazine; prof; propizochlor; propisamide; prosulfalin; prosulfocarb; prosulfuron (CGA-152005); donachlor; piraflufen-ethyl (ET-751), pyrazone; pyrazosulfuron-ethyl; pyrazoxifene; pyribenzoxime, pyridate; pyriminobac-methyl (KS-6127), pyrithiobac (KIH-2031); pyroxopope and its esters (eg, propargyl ester); quinclorac; chinermac; quinofop and its ester derivatives, gisalofop and gisalofopP and its ester derivatives, e.g. gisalofop-ethyl; hyzalofop-β-tefuryl and -ethyl; renriduron; rimsulfuron (DPX-E 9636); S 275, i.e. 2- [4-chloro-2-fluoro-5- (2-propynyloxy) -phenyl] -4,5,6,7-tetrahydro-2H-indazole; secbumetone; Setoxidim; siduron; simazine; symmetries; SN 106279, i.e. 2 - [[7- [2-chloro-4 (trifluoromethyl) -phenoxy] -2-naphthalenyl] oxy] propanoic acid and methyl ester; sulfentrazone (FMC-97285, F-6285); sulfazuron; sulfometuron-methyl; sulfosate (ICI-A0224); sulfosulfuron (MON-37500), TCA; tebutam (GCP-5544); tebutyuron; tepaloxidime (BAS620H), terbacil; terbocarb; terbuchlor; terbumeton; terbutylazine; terbutrin; TFH 450, i.e., 14, N-diethyl-3 - [(2-ethyl-6-methylphenyl) sulfonyl] -1,1,2,4-triazole-1-carboxamide; tenyl chlorine (NSK-850); thiazafluron; thiazopyr (Mp13200); thidiazimine SN-124085); tifensulfuron-methyl; thiobencarb; thiocarbazil; tralcosidim; tri-alate; triazulfuron; triazophenamide; tribenuron-methyl; triclopyr; tridiphane; trietazine; trifluralin; triflusulfuron and esters (e.g. methyl ester, DPX-66037); trimethuron; tsitodef; Vernolate; WL 110547, i.e. 5-phenoxy-1- [3- (trifluoromethyl) phenyl] -1Htetrazole; UBH-509; D-489; LS-82-556; KRP300; KRP-421; MT-146, NC-324; KN-218; DPXN8189; DOWCO-535; DK-8910; V-53482; PP600; MBH-001.

For use, commercially available formulations may be diluted in the usual way, e.g. in the case of spray powders, emulsifiable concentrates, dispersions and water-dispersible granules is water. Powders, soil pellets and so on. for spreading as well as spreading solutions prior to administration are generally not diluted with other inert substances.

The amount of herbicide of formula (I) required varies depending on the external conditions such as temperature, humidity and method of administration. It can vary widely, e.g. between 0.001 and 10 kg / ha or more of herbicide, preferably between 0.005 and 5 kg / ha.

Examples of carrying out the invention

The following examples illustrate the invention:

A. Formulation examples

a) A powder preparation was obtained by mixing 10 wt. parts of a compound of formula (II) - (VII) and / or of group B (b), or of a mixture of a herbicidal active substance of formula (I) and a safener of formula (II) - (VII) and / or group (B) and 90 wt. parts talc as inert material and are crushed in a shock mill.

b) A wettable powder, easily dispersible in water, is obtained by mixing 25 wt. parts of a compound of formula (II) - (VII) and / or of group B (b), or of a mixture of a herbicidal active substance of formula (I) and a safener of formula (II) - (VII) and / or group In (b), 64 wt. parts of kaolin-containing quartz as aggregate, 10 wt. parts of potassium ligninsulfonate and 1 wt. part of sodium oleoylmethyl-urinate as a wetting and dispersing agent and ground into a pin mill.

c) Concentrate readily dispersible and easily suspendable in water is obtained by mixing 20 wt. parts of a compound of formula (II) - (VII) and / or of group B (b), or of a mixture of a herbicidal active substance of formula (I) and a safener of formula (II) - (VII) and / or group In (b), with 6 wt. parts of alkylphenolpolyglycoleter (®Triton X 207), 3 wt. parts of isotridecanolpolyglycol ether (8 EC) and 71 wt. parts of paraffin mineral oil (boiling range, e.g., about 255 ° C to above 277 ° C) and milled in a ball mill to a particle size below 5 μ.

d) An emulsifiable concentrate is obtained from 15 wt. portions of a compound of formula (II) (VII) and / or of group B (b), or a mixture of a herbicidal active substance of formula (I) and both a protecting agent of formula (II) - (VII) and / or of group B (B), 75 wt. parts of cyclohexanone as solvent and 10 wt. parts of oxetylated nonylphenol as an emulsifier.

e) Water-dispersible granules are prepared by mixing 75 wt. parts of a compound of formula (II) - (VII) and / or of group B (b), or of a mixture of a herbicidal active substance of formula (I) and a safener of formula (II) - (VII) and / or group In (b), 10 wt. parts of calcium ligninsulphonate, 5 wt. parts of sodium lauryl sulfate, 3 wt. parts of polyvinyl alcohol and 7 wt. parts of kaolin are ground in a pin mill and the powder is granulated into a fluidized bed by spraying with water as a granulating liquid.

f) Water-dispersible granules are prepared and homogenized and crushed in advance in one colloidal mill. parts of a compound of formula (II) - (VII) and / or of group B (b), or of a mixture of a herbicidal active substance of formula (I) and a safener of formula (II) - (VII) and / or group In (b), 5 wt. parts of sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, 2 wt. parts of sodium oleoylmethyl-urinate, 1 wt. polyvinyl alcohol, 17% by weight parts of calcium carbonate and 50 wt. parts of water are then milled in a pearl mill and the suspension thus obtained is pulverized and dried in a spray tower by means of a one-component nozzle.

Biological examples

1. Experiments in a greenhouse

1.1. Before germination

Seeds, respectively, of sprouts of one- and two-week-old harmful and useful plants are planted in pots with a diameter of 9 to 13 cm in sandy clay soil and covered with soil. Alternatively, for the rice test, rice plants are cultivated as well as plants that are harmful to the crop in water-saturated soil. The herbicides and safeners formulated as emulsifiable concentrates or powders are applied in the form of aqueous dispersions or suspensions, respectively, emulsions having a flow rate of water converted from 300 to 800 ha / ha in different dosages on the surface of the roof soil or in the test with rice is served with water for irrigation. The pots are then placed in greenhouses to further cultivate the plants under optimal conditions. The visual assessment of damage to useful and harmful plants is done 3-4 weeks

Table 5.

after treatment. The rating is expressed as a percentage of the untreated controls.

The results of the studies are presented in Tables 5 and 6 (ai = active substance)

Consumption: 200-400 g a.i./ha; herbicide 1-1; corn

product herbicide / preservative exp. [g a.i / ha] phytotox. On maize [%] Felix variety Dea variety herbicide 1-1 400 85 80 herbicide 1-1 300 85 85 herbicide 1-1 200 78 78 herbicide 1-1 / fuse b-1 300 + 300 50 40 herbicide 1-1 / fuse c-1 300 + 300 70 55 herbicide 1-1 / c-3 fuse 300 + 300 45 45 herbicide 1-1 / fuse c-7 300 + 300 35 25 herbicide 1-1 / c-10 fuse 300 + 300 40 38

Table 6. Consumption amount: 100-300 g a.i./ha; herbicide 1-1;

Action on grasses /: weeds

product herbicide / preservative exp. [g a.i./ha] action [%] ECHCG SETVI ABUTH PHBPU herbicide 1-1 300 99 100 98 90 herbicide 1-1 / def. B-1 300 + 300 99 100 99 90 herbicide 1-1 / def. c-1 300 + 300 99 100 98 85

herbicide 1 -1: herbicide example no. 1 1 (from Table 1) fuse b-1: 1- [4- (2-methoxybenzoylsulfamoyl) phenyl] -3-methylurea fuse c-1: 2-methoxy-14 [4- (2-methoxybenzoylsulfamoyl) phenyl] -acetamide c-3 fuse: N- [4- (2-methoxybenzoylsulfamoyl) phenyl] -cyclobutanecarboxamide fuse c-7: Ν- [4- (2-χποροbenzoylsulfamoyl) phenyl] -cyclopropanecarboxamide 4-isopopanecarboxamide 4-isopropanecarboxamide 4-isopopanecarboxamide 4-isopopanecarboxamide -τρπφluoromethoxybenzoyl-sulfamoyl) phenyl] -cyclopropanecarboxamide

ECHCG: Echinocloa crus galli

ABS: Abutilon theophrasti PHBPU: Pharbitis purpureum SETVI: Setaria viridis

1.2. After germination

Seeds, respectively, Germs of one- and two-week-old harmful and useful plants are planted in pots with a diameter of 9 to 13 cm in sandy clay soil and covered with soil. Alternatively, for the rice test, rice plants are cultivated as well as plants that are harmful to the crop in water-saturated soil. In a three-stage developmental stage, ie Approximately 3 weeks after the start of cultivation, the test plants are treated with the herbicides and safeners, which are formulated as emulsifiable concentrates or dusters and in the form of aqueous dispersions or suspensions, respectively, emulsions with a water consumption rate of 300 to 800 l / ha in different doses they are sprayed on the green part of the plants or in the rice test they are sprayed with water for watering. The pots are then placed in greenhouses to further cultivate the plants under optimal conditions. Visual assessment of damage to beneficial and harmful plants is made 3-4 weeks after treatment. The results of 5 studies are presented in Tables 7 to 9.

Table 7. Consumption amount: 100-300 g a.i./ha; herbicide 3-1; wheat

product herbicide / preservative dose [kg a.i./ha] damage [%] wheat (Ralle variety) herbicide 3-1 300 40 herbicide 3-1 200 35 cheobias 3-1 100 30 herbicide 3-1 / fuse I-9 300+ 150 10 herbicide 3-1 / fuse P-9 200 + 100 5 herbicide 3-1 / fuse P-9 100 + 50 0 herbicide 3-2 300 45 herbicide 3-2 200 30 herbicide 3-2 100 30 herbicide 3-2 / fuse P-9 300 + 300 10 herbicide 3-2 / fuse P-9 200 + 200 0 Herbicide 3-2 / safety p-9 100 + 100 0

Table 8, Consumption amount: 100-300 g a.i./ha; Herbicide 1-1; corn

product herbicide / preservative exp. [g a.i./ha] fitit. on maize [%] Felix variety Dea variety herbicide 1-1 100 13 15 herbicide 1-1 300 45 30 herbicide 1-1 / fuse b-1 300 + 300 13 3 herbicide 1-1 / fuse c-1 300 + 300 5 18 herbicide 1-1 / fuse P-9 300 + 300 10 20

Table 9, Consumption amount: 500 g a.i./ha; herbicide 3-1; corn

product herbicide / preservative exp. [g a.i./ha] fitit. on maize [%] Felix variety Dea variety herbicide 3-1 500 23 15 herbicide 3-1 / fuse c-1 500 + 500 10 0 herbicide 3-1 / fuse P-9 500 + 500 5 0 herbicide 3-1 / fuse P-9 500+ 1000 0 0

Herbicide 1-1: Herbicide Example No. 1-1 (from Table 1)

Herbicide 3-1: Herbicide Example No. 3-1 (from Table 3)

Herbicide 3-2: Herbicide Example No. 3-2 (from Table 3)

Fuse 9-9: 5,5-diphenyl-2-isoxazoline-3-carboxylic acid ethyl ester

L-1 Fuse: 1- [4- (2-Methoxybenzoylsulfamoyl) phenyl] -3-methylurea

C-1 Safety: 2-Methoxy-N [4- (2-methoxybenzoyl-sulfamoyl) phenyl] -acetamide

2. Field attempts

Field trials are conducted on plots of 8 to 10 m ^{2 in size,} and each experiment is repeated 2 to 4 times. After sowing the cultivated plants, prior to emergence in leaf stage 2-6, the experimental preparations are applied with the help of separate sprayers for each plot. The spraying volume is from 100-300 Ι / ha of water and is applied with flat jet nozzles at 2-3 pressure. bar. A visual assessment is made. The pro5 cent scale (0-100%) assesses the effect on cultivated plants, respectively on grasses and weeds relative to untreated control plants. After administration, 2-3 evaluations are made at intervals of 7, 14, 28, 42 days.

The results represent averages of

2-4 reps. In general, maize damage is accepted up to 15%. Weed action should show an efficacy rate of> 60%. From the sowing to the end of the experiments, the plants are exposed to the climatic conditions (rainfall, temperature, humidity) that are characteristic of the experimental sites.

The test results are presented in Tables 20 to 10 to 13 (dat: = days after treatment)

Table 10 »Field Experience: 4-leaf maize application (after germination)

product herbicide / preservative exp. [g a.i./ha] phytotox. on a tsar. [%] 14 dat 31 dat herbicide 1-1 105 35 12 herbicide 1-1 / fuse P-9 105 + 100 7 0 fuse P-9 100 0 0

Table 11, Field Experience: Application in 4th leaf stage, maize

product herbicide / preservative exp. [g a.i./ha] phytotox. on a tsar. [%] 14 dat 42 dat herbicide 1-1 50 42 18 herbicide 1-1 / fuse1 1-9 50 + 120 8 2 fuse I-9 120 0 0

Table 12 Action on grass / weeds (after emergence)

product herbicide / preservative space [g a.i./ha] phytotoxicity [%] corn Panicum minor Setaria faberi Abutilon theophrasti herbicide 1-1 105 35 75 75 72 herbicide 1 -1 / def. I-9 105 + 100 7 72 83 73 fuse I-9 100 0 0 0 0

Table 13. Mixture with sulfonylureas (after germination)

product herbicide / preservative exp [g a.i./ha] fitotok. on maize [%] 14 dat 42 dat herbicide 1-1 50 42 18 herbicide 2 120 13 7 herb. 1-1 + herb. 2+ Dozens I-9 50 + 120 + 120 10 5 fuse P-9 120 0 0

herbicide 1 -1: herbicide example no. 1 1 (from Table 1) herbicide 2: N, N-dimethyl-2- [3- (4,6 dimethoxypyrimidin-2-yl) -ureidosulfonyl] 4-formylaminobenzamide

Fuse 9-9: ethyl ester

5,5-diphenyl-2-isoxazoline-3-carboxylic acid

Claims (12)

Claims A herbicidal active agent comprising a mixture of A. an herbicidal active amount of one or more compounds of formula (I) wherein V is a radical of the group (VI) to (V4), (VI) (V2) with symbols and indices having the following meanings: R is hydrogen, (C ₁ -C ₄ ) -alkoxycarbonyl, (C 1 -C ₄ ) -halo-alkoxycarbonyl, (C 1 -C ₄ ) alkylsulfonyl, (C ₃ -C ₄ ) -alkylsulfinyl, (C ₁ -C ₄ ) -alkylthio , COOH, cyano; R ¹ is hydrogen, (C ₁ -C ₄ ) -alkyl, (C ₂ -C ₄ ) -alkenyl, (C ₂ -C ₄ ) -alkynyl, (C ₃ -C ₈ ) -cycloalkyl, (C ₃ -C) ₈ ) -cycloalkenyl, (C ₁ -C ₄ ) -alkyl- (C ₃ -C ₈ ) cycloalkyl, (C ₃ -C ₇ ) -halogenocycloalkyl, (C 1 -C ₄ ) -alkylthio- (C ₃ -C ₈ ) -cycloalkyl, (C 1 -C ₈ ) haloalkyl or (C ₂ -C ₈ ) -haloalkenyl; R ² is hydrogen, (C 1 -C ₄ -alkyl, (C ₁ -C ₄ ) -alkoxy, (C ₁ -C ₄ ) -haloalkyl, halogen, (C ₁ -C ₄ -halogenoxy, cyano, nitro; R ³ is hydrogen, (C 1 -C 4 -alkyl, (C ₂ -C ₄ ) alkenyl, (C ₂ -C ₄ ) -alkynyl, (C 1 -C 4 -haloalkyl, (C 1 -C ₄ ) -anKOKCH- ( C 1 -C ₄ ) -AHKHH, (C ₃ -C ₄ ) alkylcarbonyl, (C ₃ -C ₄ ) -alkylsulfonyl, (C 1 -C 8 -haloalkylsulfonyl, with (C ₃ -C ₄ ) -alkyl substituted or unsubstituted arylsulfonyl, c (Cj-C ^ alkyl substituted or unsubstituted arilKap6oHwi- (Cj-C ₄₎ -aaKWi or (C ₁ -C ₄₎ -alkyl-substituted or unsubstituted aryl- (C ₁ -C ₄₎ -alkyl; R ⁴ is hydrogen, (C 1 -C 4 -alkyl, (C ₂ -C ₄ ) alkenyl, (C ₂ -C ₄ ) alkynyl, (C ₁ -C ₄ ) -haloalkyl, phenyl or benzyl; R ⁵ is (C 1 -C 4) -alkyl, (C 1 -C 4 -alkoxy, (C 1 -C 4) -alkoxy- (C [-C 4) -alkyl, (C 1 -C 4 -dialkoxy (C 1 -C 4) -alkyl , (C 1 -C 4) -alkylthio, halogen, substituted or unsubstituted aryl, tetrahydropyran-4-yl, tetrahydropyran-3-yl, tetrahydrothiopyran-3-yl, 1-methylthio-cyclopropyl, 2-ethylthiopropyl or two radicals R ⁵ together denote (C 2 -C ₄ ) -alkylene; R ⁶ is hydroxy, (C 1 -C ₄ ) -alkoxy, (C 1 -C ₈ ) haloalkoxy, formyloxy, (C 1 -C 4 -alkylcarbonyloxy, (C 1 -C ₄ -alkylsulfonyloxy, (C 1 -C ₄ )) -alkylthio, (C 1 -C ₄ ) -haloalkylthio, arylthio, aryloxy, alkylsulfinyl or (C 1 -C ₄ ) alkylsulfonyl; R ⁷ is (C ₃ -C ₄ ) -alkyl, (C 1 -C 4 -haloalkyl, (C ₃ -C ₈ ) -cycloalkyl, (C ₁ -C ₄ ) -alkyl- (C ₃ -C ₈ ) -cycloalkyl, or (C ₃ -C ₈ ) -halogenocycloalkyl; R ⁸ is cyano, (C ₁ -C ₄ -alkoxycarbonyl, (C ₁ -C ₆ -alkylcarbonyl, (C ₁ -C ₄ ) -alkylsulfonyl, (C ₁ -C ₄ ) -alkylsulfinyl, (C ₁ -C ₄ -alkylthio, (Cj -C 1-6 alkylaminocarbonyl or (C 1 -C ₄ ) dialkylaminocarbonyl; I is an integer from 0 to 6, and for I> 2, the radicals R ⁵ may be the same or different, and R ⁹ are the same or different and denote nitro, amino, (C ₁ -C ₆ -alkyl, (C ₂ -C ₄ ) -alkenyl, (C ₂ -C ₄ ) alkynyl, halogen, (C 1 -C 4 -haloalkyl, (C ₂ -C ₄₎ -haloalkenyl, (C ₂ -C ₄₎ haloalkynyl, (C ₁ -C ₄₎ -haloalkoxy, (Cj-C ₄₎ haloalkylthio, (Cj-C ^ alkoxycarbonyl, (C | -C ₄₎ -alkylsulfonyl, (C ₁ -C ₄ ) -alkylsulfinyl, (C ₁ -C ₄ -alkylthio, arylsulfonyl, arylsulfinyl, arylthio, (C 1 -C 4 -alkoxy, (C ₃ -C ₄ ) alkoxy- (C ₃ -C ₄ ) -alkoxy, (C 1 -C 4) -alkylthio (C 1 -C ₄ ) -anKOKCH, (C ₃ -C ₄ ) -alkylcarbonyl, (C 1 -C ₄ ) -alkylaminosulfonyl, (C 1 -C ₄ ) -dialkylaminosulfonyl, (C 1 -C 4 -alkylcarbamoyl, (C 1 -C ₄ ) -dialkylcarbamoyl, (C 1 -C 4 -alkoxy (C , -C ₄ ) -alkyl, phenoxy, cyano, aryl, alkylamino or dialkylamino; q is 0.1, 2, 3 or 4; and C. antidote action of one or more fuses in the group: (a) compounds of formulas (II) to (IV) (Π) with symbols and indices having the following meanings: n 'is an integer from 0 to 5; T is a (C 1 or C ₂ ) -alkanediyl chain, which is unsubstituted or substituted by one or two (C 1 -C 6 -alkyl radicals or by [(C 1 -C 6) alkoxy] -carbonyl; W is an unsubstituted or substituted double-stranded heterocyclic radical of the group of partially unsaturated or aromatic five-membered heterocycles with 1 to 3 heteroatoms in the N or O ring, wherein at least one atom and at most one O atom are contained in the ring , preferably a radical from rpynaTa (W1) to (W4) (W1) (W2) 1 'is 0 or 1; R ¹⁷ , R ¹⁹ are the same or different and represent halogen, (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) -alkoxy, nitro or (C 1 -C ₄ -haloalkyl; R ¹⁸ , R ²⁰ are the same or different and denote OR ²⁴ , SR ²⁴ or NR ²⁴ R ²⁵ or a saturated or unsaturated 3- to 7-membered heterocycle with at least one N atom and up to 3 heteroatoms bonded through the N atom with the carbonyl group in (II), resp. (III) and is unsubstituted or substituted by (C ₁ -C ₄ ) -alkyl, (C ₁ -C ₄ -alkoxy) radicals or optionally substituted by phenyl; R ²⁴ is hydrogen or unsubstituted or substituted aliphatic hydrocarbon radical; R ²⁵ is hydrogen, (C 1 -C ₆ ) -alkyl, (C 1 -C ₆ ) -alkoxy or substituted or unsubstituted phenyl; R ²⁶ is hydrogen, (C ^ C ^ -alkyl, (C _t -C ₈₎ -xalogenoalkil, (C, -C ₄₎ -alkoxy- (C) -C ₄₎ -alkyl, (C ^ -C ^ - hydroxyalkyl, (C ₃ -C ₁₂₎ -cycloalkyl or tri- (C _| -C ₄₎ -alkylsilyl; R ²⁷ , R ²⁸ , R ²⁹ are the same or different and represent hydrogen, (C 1 -C ₁₂ -alkyl, (C 1 -C ₈ ) -haloalkyl, (C ₃ -C ₁₂ ) -cycloalkyl or substituted or unsubstituted phenyl; (W3) (W4) R ²¹ is (C ₁ -C ₄ ) -alkyl, (C ₁ -C ₄ -halogenoalkyl, (C ₂ -C ₄ ) -alkenyl, (C ₂ -C ₄ ) -halogenoalkenyl, (C ₃ -C ₇ ) -cycloalkyl; R ²² , R ²³ are the same or different and represent hydrogen, (C 1 -C ₄ ) -alkyl, (C ₂ -C ₄ ) -alkenyl, (C ₂ -C ₄ ) -alkynyl, (C] -C ₄ ) -haloalkyl, (C ₂ -C ₄ ) -halogenalkenyl, (C 1 -C ₄ ) -alkylcarbamoyl- (C 1 -C ₄ ) -alkyl, (C ₂ -C ₄ ) -alkenylcarbamoyl- (C ₁ -C ₄ ) -alkyl, (C 1 -C 4 -alkoxy-C ₁ -C ₄ -alkyl, dioxolanyl- (C ₁ -C ₄ ) -alkyl, thiazolyl, furyl, furylalkyl, thienyl, piperidyl, substituted or unsubstituted phenyl, or R ²² and R ²³ form together a substituted or unsubstituted heterocyclic ring, preferably an oxazolidine, thiazolidine, piperidine, morpholine, hexahydropyrimidine or benzoxazine ring; B) one or more compounds of the group: 1,8-Naphthalic acid anhydride, methyl-diphenylmethoxyacetate, cyanomethoxyimino (phenyl) acetonitrile (cyometrinil), 1,3-dioxolan-2-ylmethoxyimino (phenyl) acetonitrile (oxabetrinil), 4'-chloro-2,2,2-trifluoroacetophenone33 1,3-1,3-daoxolan-2-ylmethyloxime (fluxofenim), 4,6-dichloro-2-phenylpyrimidine (phenlorim), benzyl-2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate (Pigago), 5 2-dichloromethyl-2-methyl-1,3-dioxolane (MG-191), Ν- (4-ΜβτΗπφβΗΗπ) -Ν '- (1-methyl-1-phenylethyl) urea (dymron) 1- [4- (N-2-methoxybenzoylsulfamo-10 yl) phenyl] -3-methylurea, 1- [4- (N-2-methoxybenzoylsulfamoyl) phenyl] -3,3-dimethylurea, 1- [4- (N-4,5-dimethylbenzoylsulfamoyl) phenyl] -3-methylurea, 15 1- [4- (N-naphthoylsulfamoyl) phenyl] -3,3 (4-chlorophenoxy) acetic acid, (R, S) -2- (4-chloro-o-tolyloxy) propionic acid (mecoprop), 4- (2,4-dichlorophenoxy) butyric acid (2,4-DB), (4-chloro-o-tolyloxy) acetic acid (MCPA), 4- (4-chloro-o-tolyloxy) butyric acid, 4- (4-chlorophenoxy) butyric acid, 3,6-dichloro-2-methoxybenzoic acid (dicamba), 1- (ethoxycarbonyl) ethyl-3,6-dichloro-2-methoxybenzoate (lactidichlor) as well as their salts, esters; c) N-acylsulfonamides of the formula (V) dimethylurea, and their salts, (2,4-dichlorophenoxy) acetic acid (2,4-D), wherein R ³⁰ is hydrogen, a hydrocarbon radical, a hydrocarbon radical, a hydrocarbon radical or a heterocyclic radical , each of the last 4 mentioned radicals being unsubstituted or substituted by one or ₃ θ more identical or different radicals of the group, halogen, cyano, nitro, amino, hydroxy, carboxy, formyl, carbonamide, sulfonamide and radicals of the formula Z ^a- R ^a , with each hydrocarbon moiety containing ₃ 5 preferably 1 to 20 C atoms and one C - containing the radical R ³⁰ , together with the substituents, preferably contains 1 to 30 C atoms; R ³¹ is hydrogen or (C 1 -C 6 alkyl) or R ³⁰ and R ³¹ together with the group of the formula up to CO-N- is a radical of one 3- to 8-membered saturated or unsaturated ring; R ³² is identical or different halogen, cyano, nitro, amino, hydroxy, carboxy, formyl, CONH _2, SO ₂ NH ₂ or a radical of 45 formula Z ^b -R ^b; R ³³ is hydrogen or (C 1 -C ₄ ) -alkyl; R ³⁴ is the same or different and represents halogen, cyano, nitro, amino, hydroxy, carboxy, CHO, CONH ₂ , SO ₂ NH ₂ or a radical of 59 formula Z ^c- R ^c ; R ^a is a hydrocarbon radical or a heterocyclic radical, each of the last two mentioned radicals being unsubstituted or substituted by one or more, the same or different radicals in the group halogen, cyano, nitro, amino, hydroxy, mono- and di-KC, - ^ ) alkyl] -amino, or is an alkyl radical in which several, preferably 2 or 3, non-adjacent Ca groups are respectively replaced by an oxygen atom; R ^b , R ^c are the same or different and denote a hydrocarbon radical or heterocyclyl, each of the two radicals mentioned above being unsubstituted or substituted by one or more identical or different radicals in the group halogen, cyano, nitro, amino, hydroxy, phosphoryl, xanoreH - (C 1 -C ₄ ) -anKOKCH, mono- and di - [(C 1 -C ₄ ) -alkyl] -amino, or an alkyl radical in which several predominantly 2 or 3, non-adjacent CH ₂ groups are replaced by respectively one oxygen atom; Z ^a is a divalent group of the formula O, S, CO, CS, CO-O, CO-S, O-CO, S-CO, SO, SO ₂ , NR *, CO-NR *, NR * -CO, SO ₂ -NR * or NR * -SO ₂ , as represented on the right of the corresponding divalent group is the bond to R _a , the radicals R * in the last mentioned 5 radicals being independently H, (C 1 -C ₄ ) -alkyl or halo- (C C ₁ -C ₄ -alkyl; Z ^b , Z ^c are independently a direct bond or a divalent group of the formula O, S, CO, CS, CO-O, CO-S, O-CO, SOCO, SO, SO2, NR *, SO2-NR *, NR * -SO2, CONR * or NR * -CO, in the case of asymmetric divalent groups, the right atom is attached to the radical R ^b , respectively R ^c and wherein the radicals R * in the last mentioned 5 radicals are independently of one another H, (C 1 -C 4) -alkyl or halo-C 1 -C 4 -alkyl; η is an integer from 0 to 4, and t is an integer from 0 to 5; d) acylsulfamoylbenzoic acid amides is the general formula (VI), optionally also in the form of salts (VI) wherein X ³ is CH or N; R ³⁵ is hydrogen, heterocyclyl or a hydrocarbon radical, the two last mentioned radicals being optionally substituted by one or more, the same or different radicals of the group halogen, cyano, nitro, amino, hydroxy, carboxy, CHO, CONH ₂ , SO ₂ NH ₂ and Z ^d -R ^d ; R ³⁶ is hydrogen, hydroxy, (C ₁ -C ₆ ) -alkyl, (C ₂ -C ₆ ) -alkenyl, (C ₂ -C ₆ ) -alkynyl, (C 1 -C ₆ ) -alkoxy, (C ₂ -C ₆ ) -alkenyloxy, the five last mentioned radicals being optionally substituted by one or more identical or different radicals of the group halogen, hydroxy, (C 1 -C ₄ ) -alkyl, (C ₁ -C ₄ ) -alkoxy and ( C 1 -C ₄ ) -alkylthio, or R ³⁵ and R ³⁶ together with the nitrogen atom bearing them form a 3- to 8-membered saturated or unsaturated ring; R ³⁷ is the same or different and represents halogen, cyano, nitro, amino, hydroxy, carboxy, CHO, CONH ₂ , SO ₂ NH ₂ or Z ^is -R ^e ; R ³⁸ is hydrogen, (C ₁ -C ₄ ) -alkyl, (C ₂ -C ₄ ) -alkenyl, (C ₂ -C ₄ ) -alkynyl; R ³⁹ is the same or different and stands for halogen, cyano, nitro, amino, hydroxy, carboxy, phosphoryl, CHO, CONH ₂ , SO ₂ NH ₂ or Z ^f -R ^f ; R ^d is a (C ₂ -C ₂₀ ) -alkyl radical whose hydrocarbon chain is interrupted singly or repeatedly by oxygen atoms, heterocyclyl or hydrocarbon radicals, the two last 25 mentioned radicals being optionally substituted by one or more identical or different radicals of the group halogen, cyano, nitro, amino, hydroxy, mono- and di - [(C 1 -C ₄ ) alkyl] -amino; R ^e , R ^f are the same or different and denote a (C ₂ -C ₂₀ ) -alkyl radical whose hydrocarbon chain is interrupted singly or repeatedly by oxygen atoms, heterocyclyl or a hydrocarbon radical, the two last mentioned radicals being optionally substituted by one or more identical or different radicals from the group halogen, cyano, nitro, amino, hydroxy, phosphoryl, (C ₁ -C ₄ ) -haloalkoxy, mono- and di - [(C ₁ -C ₄ ) -alkyl] -amino; Z ^d is a divalent radical of the group 0, S, CO, CS, C (O) O, C (O) S, SO, SO ₂ , NR *, C (O) NR * or SO ₂ NR *; Z ^e , Z ^f are the same or different and denote a direct bond or a divalent radical of the group O, S, CO, CS, C (O) 0, C (O) S, SO, S0 ₂ , NR *, SO ₂ NR * or C (O) NR *; R * is hydrogen, (C 1 -C ₄ ) -alkyl or (C 1 -C ₄ ) haloalkyl; s is an integer from 0 to 4, and o in the case where X is CH, denotes an integer from 0 to 5, and in the case where X is N, denotes an integer from 0 to 4; including stereoisomers and salts customary to agriculture, excluding mixtures containing a) 4- [2-chloro-3- (4,5-dihydroisoxazole- 3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy-1H-pyrazole and 2,4-D, 4- [2-chloro-3- (4,5-dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydro-5 roxy-1H-pyrazole and S-metolachlor, 4- [2-chloro-3- (4,5-dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy-1H-pyrazole and dicamba, 4- [2-chloro-3- (4,5-dihydroisoxazol-3- 10 yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy-1H-pyrazole and MCPA, 4- [2-chloro-3- (4,5-dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy-1H-pyrazole and cloquintocet, 15 4- [2-chloro-3- (4,5-dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1-ethyl-5-hydroxy-1H-pyrazole and dicamba, 4- [3- (4,5-dihydroisoxazol-3-yl) -2-methyl-4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy-20-roxy-1H-pyrazole and acetochlor, 4- [3- (4,5-dihydroisoxazol-3-yl) -2-methyl-4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy-1H-pyrazole and S-metolachlor, 4- [3- (4,5-dihydroisoxazol-3-yl) -2-methyl-25-yl-4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy-1H-pyrazole and dicamba, (b) in the compound of formula (I) V = VI or V4 and the safener is of formula (IV) or is selected from the group 30 1,8-naphthalic acid anhydride; methyl-diphenylmethoxy-acetate; 2-dichloromethyl-2-methyl-1,3-dioxolane; cyanomethoxy-imino (phenyl) -acetonitrile; 1,3-dioxolan-2-ylmethoxyimino- (phenyl) -acetonitrile; 4'-chloro-2,2,2-trifluoroacetophenoneO-1,3-dioxolan-2-ylmethyloxime; 4,6-dichloro-2-phenylpyrimidine; benzyl-2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate and (5-chloro-8-quinolinoxy) acetic acid 1-methyl-hexyl ester; or c) in the compound of formula (I) V = V3 with R ⁶ = OH and the safety lock is - of formula (II) with W = W1, W2, W3 or W4 with m '= 1, or - of formula (III) and T is one (C _} - or C ₂ -) -alkanediyl chain which is unsubstituted or substituted by one or two (C ₁ -C ₄ ) -alkyl radicals, or is of formula (IV), or - compound of the 1,8 naphthalic acid anhydride group, oxabetrinil, cyanomethoxyimino (phenyl) acetonitrile, fluxofenim and flurazole. The herbicidal active agent of claim 1, wherein in a compound of formula (I) V means a radical from group (VI) to ( ^V1 ) (V2) (V4) with symbols and indices having the following meanings: R is hydrogen, (C1-C4-alkoxycarbonyl; 45 R ¹ is (C ₃ -C ₇ ) -cycloalkyl, (C 1 -C 6 -alkyl (C ₃ -C ₇ ) -cycloalkyl; R ² is hydrogen; R ³ is hydrogen, (C 1 -C ₄ ) -alkyl, with (C ₁ -C ₄ ) alkyl substituted arylsulfonyl, (C 1 -C ₄ ) -alkyl-50 arylcarbonylmethyl, benzyl; R ⁴ is (C 1 -C ₄ ) -alkyl; R ⁵ is (C 1 -C 4) -alkyl, (C 1 -C 4) -alkoxy or two radicals R ⁵ is C 2 -alkenyl; R ⁶ is hydroxy, (C 1 -C ₄ ) -alkoxy, phenylthio; R ⁷ is (C ₃ -C ₇ ) -cycloalkyl; R ⁸ is cyano; I is an integer from 0 to 3, where for I> 2 the radicals R ⁵ may be the same or different from each other, and R ⁹ are the same or different and represent (C 1 -C 4 -alkyl; halogen, nitro, (C 1 -C ₄ ) -haloalkyl, (C 1 -C 6 -halogenoalkoxy, (C 1 -CJ-alkylsulfonyl, (C 1 -C 4) -alkylsulfonyloxy, (C ₁ -C ₄ ) -alkylsulfonylamino, (C 1 -C 4 -alkoxycarbonyl; q is 0, 1, 2 or 3. A herbicidal active agent according to claim 1 or 2, comprising a fuse of formula (II) and / or (III), wherein the symbols and indices have the following meanings: R ¹⁸ , R ²⁰ ca OR ²⁴ ; R ²⁴ is hydrogen, (C ₁ -C ₁₈ ) -alkyl, (C ₃ -C ₁₂ ) cycloalkyl, (C ₂ -C ₈ ) -alkenyl and (C ₂ -C ₁₈ ) -alkynyl, such as the C-containing groups may be substituted by one or more R ⁵⁰ radicals; R ⁵⁰ is the same or different and stands for halogen, hydroxy, (C 1 -C 8) -alkoxy, (C 1 -C 8) alkylthio, (C 2 -C 8) -alkenylthio, (C 2 -C 8) -alkynylthio, (C 2 -C 8) -alkenyloxy , (C2-C8) -alkynyloxy, (C3-C7) -cycloalkyl, (C3-C7) -cycloalkoxy, cyano, mono- and di- (C1-C4) -alkyl) -amino, carboxy, (C1-C8) -alkoxycarbonyl, (C2-C8) -alkenyloxycarbonyl, (C1-C8) -alkylthiocarbonyl, (C2-C8) -alkynyloxycarbonyl, (C1-C8) -alkylcarbonyl, (C2-C8) -alkenylcarbonyl, (C2-C8) alkynylcarbonyl, 1- (hydroxyimino) - (C 1 -C 6) -alkyl, 1 - [(C 1 -C 4) -alkylimino] (C 1 -C 6 -alkyl, 1 - [(C 1 -C 4) -alkoxyimino] (C 1 -C 4) -alkyl, (C 1 -C 6 -alkylcarbonylamino, (C 2 -C 8) alkenylcarbonyl but, (C2-C8) -alkynylcarbonylamino, aminocarbonyl, (C 1 -C 8) alkylaminocarbonyl, di- (C 1 -C 6) -alkyl-aminocarbonyl, (C 2 -C 6) -alkenylaminocarbonyl, (C 2 -C 6) -alkynyl-alkylcarbonyl, Cl BD-alkoxycarbonylamino, (C ^ -C ^ -alkilaminokarbonilamino, (C1-C6) -alkylcarbonyloxy which is unsubstituted or is substituted with R ^51, (S2S ₆₎ -alkenilkarboniloksi, (C ₂ -C ₆₎ -alkinilkarboniloksi , (C ₁ -C ₈ ) -alkylsulfonyl, phenyl, phenyl- (C 1 -C ₆ ) -alkoxy, phenyl- (C ₁ -C ₆ ) -alkoxycarbonyl, phenoxy, phenoxy- (C ₁ -C ₆ ) -alkoxy , phenoxyDi-Cd-alkoxycarbonyl, phenylcarbonyloxy, phenylcarbonylamino, phenyl (C 1 -C ₆ ) -alkyl carbonylamino, wherein the last mentioned 9 radicals are not substituted in the phenyl ring or are mono- or polysubstituted by the radicals R ⁵² ; SiR ' ₃ , OSiR' ₃ , R'jSi-iCj-C ^ -anKOKCH, CO-O-NR ' ₂ , ON = CR' ₂ , N = CR ' ₂ , ON-R' ₂ , NR ' ₂ , CH (OR ') ₂ , O (CH ₂ ) _w -CH (OR') ₂ , CR '"(OR') ₂ , O (CH ₂ ) _w CR"'(OR") ₂ or c R" O-CHR "'CHCOR" (C 1 -C 6 -alkoxy, R ⁵¹ is the same or different and denotes halogen, nitro, (C 1 -C 6 -alkoxy and phenyl, unsubstituted or substituted by one or more R ⁵² radicals; R ⁵² is the same or different and denotes halogen, (C 1 -C 4 -alkyl, (C 1 -C 4 -alkoxy, (C ₃ C ₄ ) -haloalkyl, (C 1 -C 4 -haloalkyloxy or nitro; R 'is the same or different and denotes hydrogen, (C ₁ -C ₆ -alkyl, and phenyl, unsubstituted or substituted by one or more radicals R ⁵² , or two radicals R' form together a (C ₂ -C ₆ ) alkanediyl chain; R 'is the same or different and means (C 1 -C ₄ ) -alkyl, or two radicals R' form together a (C ₂ -C ₆ ) -alkanediyl chain; R '' is hydrogen or (C 1 -C ₄ ) -alkyl; w is 0, 1, 2, 3, 4, 5 or 6. A herbicidal active agent according to claim 1 or 2, containing safeners of the formula (V) or salts thereof, wherein R ³⁰ is hydrogen, (C 1 -C ₆ -alkyl, (C ₃ -C ₆ ) -cycloalkyl, furanyl or thienyl, each of the last-mentioned 4 radicals is unsubstituted or substituted with one or more substituents from the group halogen, (C ^ -C ^ alkoxy, halo (Cj-C ^ alkoxy and (C ₁ -C ₄₎ -alkylthio and the case of cyclic radicals, also with (C 1 -C) alkyl and (C 1 -CJ) haloalkyl, R ³¹ is hydrogen, R ³² is halogen, halogen- (C ₁ -C ₄₎ -alkyl, halo- _(C) -C ₄₎ -alkoxy, (C ₃ -C ₄₎ -alkyl, (C-C) alkoxy, (C C 1-6 alkylsulfonyl, (C ₁ -C ₄ ) -alkoxycarbonyl or (C ₁ -C ₄ ) -alkylcarbonyl, preferably halogen, (C 1 -C 4 -halogenoalkyl such as trifluoromethyl, (C 1 -C 4 -alkoxy, halogen (C 1 - C 1 -C 6 alkoxy, (C 1 -C 6 -alkoxycarbonyl or (C 1 -C 6 -alkylsulfonyl, R ³³ is hydrogen, R ³⁴ is halogen, (C ₍ -C ₄ ) -alkyl, halogen (C ₁ -C ₄ ) -alkyl, halogen- (C ₁ -C ₄ ) -alkoxy, (C ₃ -C ₆ ) -cycloalkyl, phenyl, (C ₁ -C ₄ ) -alkoxy, cyano, (C ₁ -C ₄ ) -alkylthio, (C ₁ -C ₄ ) -alkylsulfinyl, (C ₁ -C ₄ -alkylsulfonyl, (C ₁ -C ₄ ) -alkoxy carbonyl or (C 1 -C 1 -alkylcarbonyl, preferably halogen, (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) -halogenoalkyl such as trifluoromethyl, halosene (1 -C ₄ ) -alkoxy, (C] -C ₄ ) -alkoxy or (C _t -C ₄₎ -alkylthio, η is 0, 1 or 2 and 5 or 2 tel. The herbicidal active agent according to claim 1 or 2, comprising a fuse of formula (VI), wherein X ³ eCH; Yu R ³⁵ is hydrogen, (C 1 -C ₆ -alkyl, (C ₃ -C ₆ ) cycloalkyl, (C ₂ -C ₆ ) -alkenyl, (C ₅ -C ₆ ) -cycloalkenyl, phenyl or 3- to 6-membered heterocyclyl of up to three heteroatoms in the nitrogen, oxygen and sulfur groups, the last six mentioned radii being optionally substituted by one or more identical or different substituents on the halogen, (C 1 -C ₆ ) -alkoxy, (C ₁ -C ₆₎ -haloalkoxy, (C] -C ₂₎ -alkylsulfinyl, (C _t -C ₂₎ -ankilsulfonil, (C ₃ -C ₆₎ -cycloalkyl, (C] _-C4) -al- 20 alkoxycarbonyl, (C ₁ -C ₄ ) alkylcarbonyl and phenyl and in the case of cyclic radicals and with (C 1 -C ₄ ) alkyl and (C ₁ -C ₄ ) -haloalkyl; R ³⁶ is hydrogen, (C 1 -C ₆ ) -alkyl, (C ₂ -C ₆ ) -alkenyl, (C ₂ -C ₆ ) -alkynyl, the three last 25 mentioned radicals being optionally substituted by one or more identical or different radicals from the group halogen, hydroxy, (C 1 -C ₄ ) alkyl, (C 1 -C 4 -alkoxy and (C 1 -C ₄ ) -alkylthio; R ³⁷ is the same or different and denotes 30 halogen, (C 1 -C 4 -halogenoalkyl, (C 1 -C ₄ ) -halogaloxy, nitro, (C 1 -C ₄ ) -alkyl, (C ₁ -C ₄ ) - alkoxy, (C ₁ -C ₄ -alkylsulfonyl, (C 1 -C ₄ ) -alkoxycarbonyl or (C ₁ -C ₄ ) -alkylcarbonyl; R ³⁸ is hydrogen; 35 R ³ 'is the same or different and stands for halogen, nitro (C 1 -C ₆ -alkyl, (C ₁ -C ₆ -halogenoalkyl, (C ₁ -C ₄ ) -haloalkoxy, (C ₃ -C ₆ ) cycloalkyl, phenyl, (C 1 -C ₄ ) -alkoxy, cyano, (C 1 -C ₄ ) -alkylthio, (C 1 -C ₄ ) -alkylsulfinyl, (C 1 -C ₄ ) -alkylsulfonyl, (C 1 -C ₄ ) - alkoxycarbonyl or (C ₁ -C ₄ ) -alkylcarbonyl; s is 0, 1 or 2 and o is 1 or 2. A herbicidal active agent according to one or more of claims 1 to 5, in which the weight ratio of herbicide: fuse is 1: 100 to 100: 1. A herbicidal active agent according to one or more of claims 1 to 6, further comprising another herbicide. The herbicidal active agent of claim 7, wherein the additional herbicide is sulfonylurea. A method of controlling harmful plants in crops of useful plants, characterized in that a herbicidal active amount of one herbicidal active substance according to one or more of claims 1 to 8 is applied to harmful plants, cultivated plants, plant seeds or the area on which the plants grow. A method according to claim 9, wherein the plants are from the group of maize, wheat, rye, barley, oats, rice, sorghum, cotton and soybeans. A method according to claim 9 or 10, characterized in that the plants are altered by gene technique. Use of a herbicidal active agent according to one or more of claims 1 to 8 for the control of harmful plants in crops of useful plants. Publication of the Patent Office of the Republic of Bulgaria 1797 Sofia, 52-B Dr. GM Dimitrov Blvd.